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1 © IWA Publishing 2018 Water Science & Technology | in press | 2018

Fabrication of Zr doped TiO2/chitosan composite catalysts

with enhanced visible- light-mediated photoactivity
for the degradation of Orange II dye
Pelin Demircivi and Esra Bilgin Simsek

ABSTRACT

Zirconium/Titanium/Chitosan (Zr/Ti/CHT) composite catalysts were synthesized by sol-gel method Pelin Demircivi (corresponding author)
Esra Bilgin Simsek
using different chitosan amounts (5–20 wt.%) and their activity in the photocatalytic degradation of Department of Chemical and Process Engineering,
Faculty of Engineering,
Orange II dye were evaluated for the first time. The results were compared with Zr/Ti, Zr/CHT and Yalova University,
77100 Yalova,
Ti/CHT catalysts. The composite catalysts were characterized by X-ray diffraction (XRD), fourier Turkey
transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and X-ray photoelectron E-mail: pelindemircivi@gmail.com

spectroscopy (XPS) analysis. XRD analysis revealed that the Zr/Ti/CHT composite catalyst showed
high crystallinity of anatase TiO2 phase. Photocatalytic experiments showed that adding CHT into the
catalyst structure increased the photocatalytic degradation under visible light irradiation. Also, the
first-order reaction rate constant, kapp, was calculated using Langmuir-Hinshelwood (L-H) equation.
The kapp values were found as 0.009, 0.0013, 0.012 and 0.014 min
1 for Zr/Ti, Zr/CHT, Ti/CHT and
Zr/Ti/CHT, respectively. According to stability tests, after the first cycle Orange II dye degradation was
found as 95%, while it was 37% after fifth cycle. The results showed that the composite catalyst
could be used several times for Orange II dye degradation.
Key words | chitosan, Orange II, photocatalyst, TiO2, zirconium

INTRODUCTION

Azo dyes are used in various industrial applications such as,
textile, leather, pharmaceutical, plastics, etc. (Zhang et al.
). During the dying processes, 15% of the produced
dye is released to the environment (Houas et al. ).
Having carcinogenic and mutagenic effects, dyes reveal
risks for ecosystem. Orange II, also called Acid Orange 7,
is an anionic dye, which has one azo group, one sulfonated
group and two aromatic rings in its structure. It is one of the
synthetic dyes, which causes serious problems by releasing
into the water. As the other synthetic dyes, Orange II is
poorly biodegredable and has a stable structure in different
conditions. Therefore, removal of Orange II from waste-
waters is one of the important problems from the
environmental point of view.
Elimination of Orange II was studied using adsorption
(Jin et al. ; Zhang et al. ), oxidation (Inchaurrondo
et al. ), chemical degredation (Luo et al. ; Luo
et al. ) and photocatalysis (Cai et al. ). Photocatalysis
technology is the most effective method to simultaneously
doi: 10.2166/wst.2018.298
removal of Orange II from wastewater (Liu et al. ). Tita-
nium dioxide (TiO2) is generally used as the photocatalyst,
due to its inexpensive, non-toxic and photostable properties
(Ibusuki & Takeuchi ; Zou et al. ). However, TiO2
cannot be used properly under visible light due to its large
band gap (3.2 eV for anatase TiO2). Therefore, a second
element such as zirconium, tungsten, cerium or silica can
be added to increase its photocatalytic activity under visible
light irradiation and thermal stability of the phase transition
(Tian et al. ). Zirconium is a nontoxic, biologically inert
material and has high ion-exchange capacity. Zr/Ti compo-
sites are extensively used as photocatalyst (Wang et al. ;
Zhou et al. ).
Chitosan is an abundant biopolymer, which includes
amino (
NH2) and hydroxyl (
OH) groups in its structure
makes it excellent adsorbent for the removal of organic
and inorganic compounds from wastewaters (Nawi et al.
; Sokker et al. ). Including high amount of amino
and hydroxyl groups in chitosan structure improves the
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2 P. Demircivi & E. B. Simsek | Fabrication of Zr/TiO2/chitosan for degradation of dye
photocatalytic activity of the heterogeneous photocatalyst as
the adsorption is a part of photodegredation. Hamdi et al.
() synthesized phthalocyanine/chitosan-TiO2 photocata-
lyst for the photodegredation of aniline (Hamdi et al. ).
Nawi et al. () reported that the adsorption of reactive
red 4 on chitosan/glass adsorbent. They also prepared
TiO2/chitosan/glass photocatalyst and investigated its
photocatalytic activity on reactive red 4. They found that
the adsorption capacity of chitosan/glass composite has an
effective role on photocatalyst-adsorption system (Nawi
et al. ).
In this study, a novel photocatalyst, Zr/Ti/CHT nano-
composite was synthesized for the first time and its
photocatalytic activity was investigated using Orange II
dye. Zr/Ti, Zr/CHT, Ti/CHT and Zr/Ti/CHT samples
were characterized by using XRD, XPS, SEM and FTIR.
The effects of chitosan amount, initial solution pH and cat-
alyst dosage were investigated. Besides, recycle tests were
studied to reveal the applicability of Zr/Ti/CHT as effective
photocatalyst.
MATERIALS AND METHODS
Chemical and reagents
Chitosan (degree of deacetylation of 90%), zirconium oxy-
chloride octahydrate ZrOCl2.8H2O (analytical grade),
Orange II (C16H11N2NaO4S, purity > 99%) and tetrabutly
titanate (97%) was purchased from Sigma-Aldrich. All the
reagents used in this study were of analytical grades.
Catalyst preparation
To investigate the photocatalytic activity Zr/Ti, Zr/CHT,
Ti/CHT and Zr/Ti/CHT samples were synthesized. 0.5 g
chitosan was dissolved in 50 mL 2% acetic acid solution
by overnight mixing. 20 mL tetrabutyl titanate was also dis-
solved in 40 mL ethanol with 0.5 g zirconium oxychloride
octahydrate. After 1 h mixing, the solution was added into
chitosan solution drop by drop and mixed with mechanical
stirrer. Then, Zr/Ti/CHT was dried and calcined at 500 C
for 2 h. To examine the effect of CHT on photocatalytic
activity of Zr/Ti/CHT sample, CHT weight content of the
samples were changed between 5% and 20%.
Zr/Ti was synthesized by solvothermal method. 20 mL
tetrabutyl titanate was dissolved in 40 mL ethanol with
0.5 g zirconium oxychloride octahydrate. After 30 min
mixing, 2 mL conc. HCl and 4 mL H2O was added to the
Water Science & Technology | in press | 2018
solution and mixed another 30 min. The gel was aged for
1 day and hydrothermal treatment was applied in a Teflon-
lined stainless steel autoclave at 180 C for 18 h. Then, the
products were filtrated, washed with distilled water and cal-
cined at 500 C for 2 h.
Zr/CHT sample was prepared by dropwisely adding zir-
conium oxychloride octahydrate ZrOCl2.8H2O solution
(dissolved in ethanol) into 1 wt.% chitosan solution. After
1 h mixing, the solution was dried and calcined at 500 C
for 2 h.
Ti/CHT catalyst was prepared by adding tetrabutyl tita-
nate solution (dissolved in ethanol) into 1 wt.% chitosan
solution. After 1 h mixing, the solution was dried and cal-
cined at 500 C for 2 h.
Characterization of the catalysts
Characterization of the photocatalysts were analyzed by
using several methods. X-ray diffraction (XRD) using
Rigaku D/Max-IIIC diffractometer with 1.54 Å Cu-Kα radi-
ation and a 2θ range of 10–80 . The Fourier transfer
infrared (FTIR) spectrum was recorded by Perkin Elmer
Spectrum One using attenuated total reflectance method,
in the wave number range of 600–4,000 cm
1. The surface
composition of the samples was investigated using X-ray
photoelectron spectroscopy (XPS; Thermo Scientific K-
Alpha X-ray photoelectron spectrometer). Scanning elec-
tron microscopy (SEM-EDAX) analyses were carried out
using Philips XL30 ESEM-FEG/EDAX to investigate the
surface morphology of the composites.
Determination of photocatalytic activity
The photocatalytic activity of the samples was investigated
for degradation of Orange II dye solution (10 mg L
1). The
UV-A light photocatalytic experiments were carried out
under 18 UV lamps placed into columned-shaped stainless
steel cabinet. Visible light irradiation experiments were con-
ducted in a photoreactor with two visible metal halide lights
as visible light source. To perform the experiments, 50 mL
10 mg L
1 Orange II solution was added into 0.01 g catalyst.
Before the light irradiation, the solution was mixed in dark
for 30 min to achieve adsorption-desorption equilibrium.
Samples (4 mL) were regularly collected at different time
intervals and analyzed by UV-visible spectrophotometer at
485 nm.
Solution pH (3, 6.50, 10), CHT amount (5%, 10%, 15%,
20%) and initial solution concentration (5, 10, 20 mg L
1)
effects on photocatalytic activity were investigated.
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3 P. Demircivi & E. B. Simsek | Fabrication of Zr/TiO2/chitosan for degradation of dye
Durability tests of Zr/Ti/CHT/20 were conducted by
mixing 100 mL Orange II solution (10 mg L
1) with 0.08 g
catalyst. The cycles were performed by five times and each
cycle was examined for 180 min.
RESULTS AND DISCUSSION
Characterization of catalysts
XRD patterns of Zr/Ti and Zr/Ti/CHT/20 composites were
shown in Figure 1. TiO2 has three crystalline forms (rutile,
anatase, and brookite) and among these crystal forms ana-
tase phase shows the highest photocatalytic activity
(Calatayud et al. ; Fagan et al. ). The samples
show the diffraction peaks at (101), (004), (200), (105),
(211), (204), (116), (220) and (215) corresponding tetragonal
anatase phase of TiO2. Zr/Ti catalyst did not show ZrO2
peak, which might be due to the result of small particle
size of metal oxides, which is not detectable by XRD
(Tasdemir et al. ). The presence of CHT in the structure
does not affect the crystallinity of anatase phase of TiO2,
which indicates the well dispersion of CHT over Zr/Ti/CHT
catalyst (Kim et al. ).
FTIR spectra of Zr/Ti and Zr/Ti/CHT composites were
shown in Figure 2. The band at 3,100 cm
1 defines the
adsorbed water (H-O-H) (Wan et al. ; Shao et al. ).
The band appearing at 3,155 cm
1 could be attributed to
bending N-H groups of CHT (Safari et al. ), stretching
vibrations of O-H groups and bending vibrations of Ti-OH
(Gao et al. ; Afzal et al. ). The peak around
2,182 cm
1 was assigned to stretching vibration of –CH
group. The absorption band around 700 cm
1 confirms the
existence of Ti-O-Ti groups in the Zr/Ti/CHT composite
structure (Karthikeyan et al. ).
SEM analyses are important to investigate the structural
properties of the composites. SEM images of Zr/Ti,
Figure 1 | XRD spectrum of Zr/Ti and Zr/Ti/CHT/20.
Water Science & Technology | in press | 2018
Figure 2 | FTIR spectrums of the catalysts.
Zr/CHT, Ti/CHT and Zr/Ti/CHT/20 composites were rep-
resented in Figure 3. SEM images of Zr/Ti, Zr/CHT and
Ti/CHT showed round-shaped particles on their surface,
which indicates the TiO2 particles. Zr/Ti/CHT/20 compo-
site surface preserves the same round-shape structure.
According to EDX results, Zr content in the catalyst was
found in a good agreement with Zr doping amount.
Elemental analysis of Zr/Ti/CHT/20 was done using
XPS technique and shown in Figure 4. The photoelectron
peaks for C 1s, O 1s, Ti 2p and Zr 3d were observed at bind-
ing energies of 285.9, 531, 457.7 and 181.8 eV, respectively.
The binding energies of C 1s spectral region deconvoluted
into C-OH/C-N at 285.9 eV, C-C/C ¼ C at 284.5 eV and
C-Ti at 283.4 eV during the formation of Zr/Ti/CHT/20 com-
posite (Cittadini et al. ). The binding energy of O 1s peaks
for Zr/Ti/CHT/20 composite appeared at 530 and 531 eV.
The high intensity peak of 531 eV was assigned to C ¼ O/
O
2 and low intensity peak of 530 eV was attributed to
oxygen bonded to Ti atom (Ti-O) (Lopez et al. ; Lin
et al. ; Cittadini et al. ). Besides, binding energies
indicates Ti/Zr-O and Ti/Zr-OH (Sun et al. ). In the Ti
2p region, the peak for Zr/Ti/CHT/20 composite appeared
at 457.7 eV, which indicates the lower binding energy of Ti
2p. The binding energies at 457.7 and 463.3 eV correspond
to the Ti 2p3/2 and Ti 2p1/2 levels, respectively. The peak at
binding energy at 457.7 eV is evidence of Ti3þ state. Ti 2p
spectra of Zr/Ti/CHT/20 indicate the formation of Zr-O-Ti
and also show that the Zr was well dispersed in TiO2 lattice.
In the Zr 3d spectra of Zr/Ti/CHT composite, the peak
appeared at 181.8 eV represents Zr4þ oxidation state (Wu
et al. ). The peaks at 181.8 and 183 eV indicate Zr 3d5/2.
Electron transfer between Zr4þ and Ti4þ resulted shifting in
binding energy, which indicates Zr-O-Ti formation (Badli
et al. ). The results show that the Zr was well dispersed
on the catalyst surface.
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4 P. Demircivi & E. B. Simsek | Fabrication of Zr/TiO2/chitosan for degradation of dye
Figure 3 | SEM images of the catalysts.
Adsorption and photocatalytic activity
For effective photocatalytic degradation reactions of the cat-
alyst can be achieved by the preliminary adsorption of the
pollutant (Li et al. ). Therefore, to investigate the adsorp-
tion equilibrium of the catalysts, dark adsorption
experiments were conducted by mixing 10 mg catalyst with
50 mL 10 mg L
1 Orange II solution in dark. Zr/Ti,
Zr/CHT and Ti/CHT were reached the equilibrium within
60 min, 120 min and 120 min, respectively (Figure 5 inset).
Removal efficiency of Zr/Ti catalyst was found as 25%
within 60 min. The incorporation of CHT increased the
removal efficiency of the catalysts which Zr/CHT and
Water Science & Technology | in press | 2018
Ti/CHT possess removal efficiency around 47% and 45%,
respectively. Zirconium (Zr4þ) is a positively charged
cation and has an effect on Orange II dye adsorption by
electrostatic interactions. Chitosan also includes protonated
amino group, which contributes Orange II adsorption.
Adsorption mechanism helps to increase of the photocataly-
tic activity of the catalyst by adsorbing the dye molecule to
the surface and which makes the dye molecule closer to
the active surface and increase the interaction between the
dye molecule and the catalyst, which resulted with an
increase of the dye degradation. Increasing CHT amount
in Zr/Ti/CHT catalyst was resulted with an increase in
Orange II removal. It was found that the removal
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5 P. Demircivi & E. B. Simsek | Fabrication of Zr/TiO2/chitosan for degradation of dye Water Science & Technology | in press | 2018

Figure 4 | XPS analysis results of Zr/Ti/CHT/20.

efficiencies of Zr/Ti/CHT/5, Zr/Ti/CHT/10, Zr/Ti/CHT/15

and Zr/Ti/CHT/20 as 28, 38, 46 and 50%, respectively. The
results indicate that Zr/Ti/CHT/20 catalyst has the higher
removal efficiency for Orange II dye adsorption.
To examine the photocatalytic activity of the catalyst,
the photocatalytic degradation of Orange II under UV-A
and visible light was carried out. Figures 5 and 6 show the
time vs. C/C0 plots under UV-A light irradiation and visible
light irradiation where C0 is the dye concentration at the
beginning of the photocatalytic degradation and C is the
dye concentration at time t. The degradation efficiencies of
Orange II for Zr/Ti, Zr/CHT, Ti/CHT and Zr/Ti/CHT/20
catalysts under UV-A light irradiation after 180 min were
Figure 5 | Photocatalytic degradation of Orange II dye under UV-A irradiation [C0 ¼
found as 98%, 48%, 96% and 99%, respectively. Under vis- 10 mgL

1
, solid/liquid ratio ¼ 0.2 gL

1
, natural pH](inset: Adsorption capacities

1
1
ible light irradiation, Zr/Ti/CHT/20 (84%) catalyst was of the catalyst [C0 ¼ 10 mgL , solid/liquid ratio ¼ 0.2 gL , natural pH]).

exhibited higher photocatalytic efficiency among the pre-

pared catalyst (Zr/Ti (67%), Zr/CHT (60%) and Ti/CHT
(71%)). Adding Zr into the catalyst structure increased the
photocatalytic efficiency by increasing the hydroxyl groups
on the surface, which are responsible from photocatalytic
degradation process (Kim et al. ). Karthikeyan et al.,
studied the photocatalytic activity of chitosan-TiO2 for the
degradation of cationic rhodamine B and negatively charged
congo red. Photocatalytic mechanism was explained by the
electron-hole pair, which is formed by absorption energy.
Besides, generation of electron-hole pair involves oxi-
dation-reduction process (Karthikeyan et al. ). Under
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6 P. Demircivi & E. B. Simsek | Fabrication of Zr/TiO2/chitosan for degradation of dye Water Science & Technology | in press | 2018

Table 1 | First-order rate constant kapp and correlation coefficient R2 for photodegrada-
tion of Orange II dye

Visible light
UV-A light irradiation irradiation

1
1
kapp (min ) R2 kapp (min ) R2

Zr/TiO2 0.0257 0.96 0.009 0.93

Zr/Cht 0.0038 0.98 0.001 0.94
TiO2/Cht 0.0192 0.97 0.012 0.94
Zr/TiO2/Cht (20%) 0.0427 0.98 0.014 0.91

under UV-A light irradiation represents better photocataly-

tic degradation results than visible light irradiation. The
Figure 6 | Photocatalytic degradation of Orange II dye under visible light irradiation [C0 ¼
10 mgL

1
, solid/liquid ratio ¼ 0.2 gL

1
, natural pH].
higher kapp value was observed for Zr/Ti/CHT/20 followed
by Ti/CHT. Hamdi et al. (2009) was studied photocatalytic
activity of chitosan/phthalocyanine-TiO2 on aniline.
visible light, as a result of absorbing light on the catalyst sur-
According to kinetic results, increasing phthalocyanine
face, electrons transfer to the conduction band and holes
amount was increased the kapp value from 64*10
3 h
1 to
(hþ)/electrons (e
) are exhibited. Electrons (e
) reduce O2
101*10
3 h
1. Also, the kapp value of TiO2 was found 37*-
to form superoxide radicals (O2•
), while holes (hþ) produce
10
3 h
1, which indicated that the adding phthalocyanine
OH• radicals by reacting with OH
ions. Besides, electrons
enhanced the photocatalytic activity of the catalyst
of dye molecules are excited from HOMO to LUMO state by
(Hamdi et al. ). Zainal et al. () was investigated
absorbing light and decolourization of Orange II dye occurs
the photocatalytic activity of TiO2-chitosan/glass photocata-
reacting with the radicals (Hamdi et al. ; Karthikeyan
lyst for the degradation of methyl orange dye. Increasing
et al. ; Shaban et al. a, b).
TiO2-chitosan layer on glass was resulted with an increase
in photocatalytic activity of the catalyst. Therefore, the
TiO2 þ hν ! hþ þ e
kapp values were increased from 149.1*10
3 min
1
hþ þ H2 O ! OH þHþ (1 layer) to 269.1*10
3 min
1 (4 layers) (Zainal et al. ).

hþ þ OH
! OH
Effect of pH
e
þ O2 ! O2 

Orange II þ radicals ! CO2 þ H2 O Solution pH plays an important role on degradation of dye

The kinetic results of photocatalytic degradation process
were best described by Langmuir-Hinshelwood (L-H) model
as given in Equation (1). (Kumar et al. ).
Ct
ln ¼ kapp t
Co
where kapp is the apparent pseudo-first order reaction rate
constant (min
1), C0 and Ct are the dye concentrations at
initial and time t (mg L
1), t is the reaction time (min).
Determined kapp values from the slope of ln (Ct/Co) versus
time plot of the photocatalysts were given in Table 1.
From the data reported in Table 1, using Zr/Ti/CHT/20
composite as a photocatalyst was resulted with an enhance-
ment in the photocatalytic activity. Besides, degradation
molecule, due to effect on surface properties of the catalyst
and ionization of the dye molecule. The plots of Orange II
degradation at different pH values were presented in
Figure 7. At pH 3, Orange II degradation was found as
89%. In basic medium (pH 10), degradation percentage
decreased to 38%. In acidic medium, positively charged Zr
(1)
and protonated –NH2 groups on chitosan serve available
adsorption sites for anionic Orange II dye molecule. Electro-
static attractions occur between positively charged surface
groups and negatively charged sulfonate groups of the dye
molecules. In contrast with acidic medium, electrostatic
repulsion forces would be dominant between the surface
and anionic Orange II dye molecules. Anionic dye mol-
ecules compete with OH
molecules in the solution at
higher pH values and also the surface has lower protonated
–NH2 groups. Therefore, a decrease in adsorption and

7 P. Demircivi & E. B. Simsek | Fabrication of Zr/TiO2/chitosan for degradation of dye
Figure 7 | Effect of pH on photodegradation of Orange II dye under visible light irradiation

1
[C0 ¼ 10 mgL , solid/liquid ratio ¼ 0.2 gL
degradation of Orange II was occurred. Zhang et al. ()
investigated the adsorption efficiency of chitosan/DTAC
using orange G and acid orange 7. For both of the dye mol-
ecules the highest adsorption capacity was found at pH
3. They explained the reason of maximum adsorption
capacity at lower pH values according to electrostatic inter-
actions between protonated amino molecules on chitosan
and anionic sulfonic groups of two dye molecules (Zhang
et al. ).
Effect of CHT amount
To investigate the effect of CHT amount on Orange II degra-
dation, photocataytic degradation of Orange II was
examined at different % weight ratios (5%–20%) of CHT cat-
alysts under visible light irradiation. According to Figure 8,
the highest Orange II degradation was observed using
Zr/Ti/CHT/20 (99%), followed by Zr/Ti/CHT/10 (98%),
Zr/Ti/CHT/15 (96%) and Zr/Ti/CHT/5 (89%). This was
due to increasing available adsorption sites on catalyst sur-
face by increasing CHT amount.
Figure 8 | Effect of CHT amount on photodegradation of Orange II dye under visible light

1
irradiation [C0 ¼ 10 mgL , solid/liquid ratio ¼ 0.2 gL
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Water Science & Technology | in press | 2018
Figure 5 shows adsorption performance of Zr/Ti/CHT/5,
Zr/Ti/CHT/10, Zr/Ti/CHT/15 and Zr/Ti/CHT/20 catalysts
in dark. Photocatalysis reactions occur in conjunction with
adsorption process, which enhances the photocatalytic
activity of the composites. Increasing CHT amount resulted
with an increase in adsorption sites (–NH2 groups) on the
Zr/Ti/CHT catalyst. Besides, introduction of Zr enhances
the surface OH group formation, which resulted with a
decrease in recombination of electrone-hole pairs and
increase photocatalytic degradation performance (Gao
et al. ).

1
].
Effect of initial dye concentration
Initial dye concentration has powerful effect on dye degra-
dation. Initial Orange II concentrations were changed
between 5 to 20 mg L
1 (SFig1.). Under visible light
irradiation, Orange II dye degradation of 5 mg L
1 solution
was found as 91%, while it was 84% and 33% for 10 mg L
1
and 20 mg L
1, respectively. Difference between the degra-
dation percentages depends on the occupation of active
sites by the Orange II dye molecules. Certain numbers of
active sites on catalyst were occupied by Orange II dye mol-
ecules and could be shielded by Orange II dye molecule at
higher concentrations (Debnatha et al. ), which causes
a decrease on Orange II dye degradation.
Stability of photocatalyst
Stability of photocatalyst is one of the most important par-
ameter for economical point of view (Abdelwahab &
Helaly ). After each degradation tests, the catalyst was
separated, washed with distilled water several times, dried
and reused for a new degradation experiment by adding
fresh Orange II dye solution. Degradation of Orange II
dye for the first cycle was achieved as 95% while it
decreased to 79% after fifth cycle. The result showed that
the Zr/Ti/CHT/20 photocatalyst could be used four times
for dye degradation effectively.
CONCLUSION
Photocatalytic activity of Zr/Ti/CHT was investigated under
visible light irradiation through degradation of Orange II
dye molecules. It was found that increasing the amount of
CHT enhanced the photocatalytic activity of Zr/Ti/CHT
owing to the synergestic effect of photocatalysis/adsorption

1
, natural pH]. process. Increasing CHT amount resulted with an increase
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8 P. Demircivi & E. B. Simsek | Fabrication of Zr/TiO2/chitosan for degradation of dye
in active adsorption sites on Zr/Ti/CHT catalyst surface,
which enhanced the photocatalytic activity of the catalyst.
Also, Zr has an important effect on photocatalytic activity
due to lowering the band gap of Zr/Ti/CHT catalyst by elec-
tron transfer from Zr4þ to Ti4þ. The catalyst was found more
effective in acidic medium due protonated –NH2 groups on
chitosan surface. Zr/Ti/CHT photocatalyst could be used
four times for dye degradation effectively. A highly effective
TiO2 photocatalyst was synthesized using Zr and CHT,
which can be extensively used in photocatalytic degradation
of dye molecules.
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