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Hydrothermal synthesis and characterization of Cu2+/F- Co-doped

titanium dioxide (TiO2) nanotubes as photocatalyst for methyl orange
degradation

Article  in  Science of Advanced Materials · June 2017

DOI: 10.1166/sam.2017.3071

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 Copyright © 2017 by American Scientific Publishers
All rights reserved.
Science of
Printed in the United States of America
Advanced Materials
Vol. 9, pp. 1–10, 2017
www.aspbs.com/sam

Hydrothermal Synthesis and Characterization of

Cu2+/F− Co-Doped Titanium Dioxide (TiO2 )
Nanotubes as Photocatalyst for Methyl
Orange Degradation
Mohd Hasmizam Razali1, ∗ , Ahmad Fauzi Mohd Noor2 , and Mahani Yusoff3
1
School of Fundamental Sciences, Universiti Malaysia Terengganu, 21030 Kuala Terengganu, Terengganu, Malaysia
2
School of Materials and Mineral Resources Engineering, Universiti Sains Malaysia, Engineering Campus,
14300 USM, Nibong Tebal, Pulau Pinang, Malaysia
3
Faculty of Earth Science, Universiti Malaysia Kelantan Kampus Jeli, Karung Berkunci No.100,
17600 Jeli, Kelantan, Malaysia

ABSTRACT
Cu2+ /F− co-doped titanium dioxide (TiO2 ) nanotubes were synthesized using simple hydrothermal method.
The hydrothermal was carried out at 150
C for 24 hours using commercial TiO2 powder (MERCK) as TiO2

ARTICLE
nanotubes precursor and Cu(NO3
2 and NH4 F as Cu2+ dopant and F− co-dopant respectively in 100 ml NaOH
(10 M). The co-doped TiO2 nanotubes photocatalyst were characterized by X-ray diffraction (XRD), nitrogen
gas adsorption, transmission electron microscopy (TEM) and Energy Dispersive Spectroscopy (EDS). XRD
analysis reveals a new TiO2 hexagonal phase was obtained after Cu2+ and F− co-doping. Pure TiO2 nanotubes
is anatase TiO2 (tetragonal) phase. TEM results show that the samples possessed hollow tubular morphology
with the outer diameter within 8–10 nm and several hundred nanometer in length. The surface area of Cu2+ /F−
co-doped TiO2 nanotubes was found to be higher than undoped and single metal ion (Cu2+
doped TiO2
nanotubes. However all studied nanotube samples show large surface area (≥200 m2 /g) attributed to their
hollow tubular structure. XPS study suggests the co-doping of TiO2 with Cu2+ and F− initiated the formation of
Ti3+ besides the existences Ti4+ , which assisted the photodegradation of MO. Cu2+ doping was incorporated
into interstitial positions of TiO2 lattice, while F− co-doping highly dispersed into TiO2 by replacing and occupied
the oxygen site in the TiO2 crystal lattice to form solid solution of TiO2−x Fx .
KEYWORDS:

1. INTRODUCTION performance of the TiO2 nanotubes in pentachlorophenol

Studies have indicated that TiO2 nanotubes displayed bet-
ter catalytic performance as compared to other forms
of TiO2 . For instance, Yang et al.1 and Li et al.2 dis-
covered that TiO2 nanotubes have improved properties
for photocatalytic applications compared with colloidal
and nanoparticle forms.1 2 TiO2 nanotubes contain more
abundant in  OH concentration than TiO2 /SiO2 pow-
der, which also support the feasibility of TiO2 nano-
tubes being applied on the photocatalysis. Furthermore,
researchers indicated that both extended capability of UV-
light absorption and large specific surface area of nanotube
was predominant factors for the excellent photocatalytic
∗
Author to whom correspondence should be addressed.
Email: mdhasmizam@umt.edu.my
Received: xx Xxxx xxxx
Accepted: xx Xxxx xxxx
degradation.3 Guo et al.4 found out that TiO2 nanotubes
have a better efficiency for photocatalytic degradation of
Rhodamine B and methyl orange under solar illumina-
tion than the commercialized nano P25 TiO2 (a type
of commercial TiO2 ).4 Meanwhile, Li et al.5 synthesized
Ag-doped TiO2 nanotubes for photocatalysis of gaseous
toluene.5 The composites exhibited a degradation effi-
ciency of 98%, which was higher than those of pure P25
TiO2 and Ag-doped P25 TiO2 . The large surface area and
unique tubular structure suggested that TiO2 nanotubes
would be suitable as photocatalyst.
Even though TiO2 nanotubes showed novel properties
and exhibit better photocatalytic activities compared with
other forms of TiO2 , it is only photocatalytically active
under UV irradiation region due to their wide band gap
energy. Xu et al.6 reported the band gap energy of anatase

Sci. Adv. Mater. 2017, Vol. 9, No. xx 1947-2935/2017/9/001/010 doi:10.1166/sam.2017.3071 1

 Hydrothermal Synthesis and Characterization of Cu2+ /F− Co-Doped Titanium Dioxide (TiO2 ) Nanotubes
TiO2 nanotubes is 3.25 eV, being slightly larger than bulk
TiO2 anatase (3.2 eV) and rutile TiO2 (3.0 eV).6 Due to
their large band gap energy the TiO2 only become active
under UV light, thus limits the efficiency of solar photo-
catalytic reaction, as UV light accounts for only a small
fraction (<10%) of the incoming solar energy compared
to visible light (45%). In addition another limitation of
pure TiO2 is the rapid recombination of charge carriers.
The charge pair recombination is faster than the interfacial
charge transfer, thus reducing the quantum efficiency of
photocatalysis.7 Hence more research has been conducted
in recent years to modify and develop TiO2 photocatalyst
that can work with high efficiency under UV and visible
light irradiation by doping or co-doping with metal ions
and/or non-metal ions.
According to Asahi et al.,8 in order to obtain an effi-
cient and effective photocatalyst, modified TiO2 by doping
method should be followed these requirements:8
(1) doping should produce states in the band gap of TiO2
that absorb visible light;
(2) the CB minimum of TiO2 , including subsequent impu-
rity states, should be as high as that of TiO2 or higher than
the H2 /H2 O level to ensure its photoreduction activity; and
ARTICLE
(3) the states in the gap should overlap sufficiently with
the band states of TiO2 to transfer photoexcited carriers to
reactive sites at the catalyst surface within their lifetime.
Conditions (2) and (3) require that the non-metal ions
species should be used for doping rather than metal ions,
which often give quite localized d states deep in the band
gap of TiO2 and result in recombination centres of carriers.
Nitrogen was reported to be the most promising
non-metal ion dopant in achieving visible light active
photocatalyst.9 Due to its comparable atomic size with
oxygen and small ionization energy, nitrogen can be eas-
ily introduced in TiO2 structure. In 2005, Sato discovered
that the addition of NH4 OH in the titania sol, followed
by calcination of the precipitated powder, resulted in a
nitrogen doped TiO2 material that exhibited a visible light
response.10 Since then, there have been many reports deal-
ing with nitrogen doping of TiO2 . Significant efforts have
been devoted to investigating the structural, electronic and
optical properties of nitrogen doped TiO2 , understand-
ing the underlying mechanisms and improving the pho-
tocatalytic and self-cleaning efficiency under visible and
solar light. However, nitrogen doped TiO2 are limited
by long-term instability, low reactivity and low quantum
efficiency.11 12
Shen et al.13 demonstrated that C-doped TiO2 showed
stronger absorption in the UV-visible range, attributed to
carbon substitutions at oxygen sites in the sample, and
therefore exhibited better photocatalytic activity.13 Another
factor that may account for the high visible-light photocat-
alytic activity of C-doped TiO2 is the higher surface area
of the doped samples, which could provide more active
sites and adsorb more reactive species for photodegrad-
ing pollutants in aqueous solution.14 It was found that the
2 Sci. Adv. Mater., 9, 1–10, 2017
Razali et al.
resulting carbon-doped TiO2 exhibits significantly higher
photocatalytic activity than the undoped counterpart and
Degussa P25 on the degradation of rhodamine B (RhB) in
water under visible light irradiation ( > 420 nm).
Grabowska et al.15 synthesized boron-doped TiO2 and
found out that it had lower surface area as compared to
undoped TiO2 .15 One of the important features in boron
doping is the red shift in the absorption band of TiO2 . The
formation of Ti–O–B species enables the B–TiO2 active in
phenol photodegradation under visible light irradiation.16
The incorporation of boron atoms into TiO2 matrix by
occupying O sites to form O–Ti–B induced the visible
light photocatalytic activity of B–TiO2 .17 However, beyond
an optimal doping rate, diboron trioxide phase (B) was
formed in the doped TiO2 which led to lower photocat-
alytic activity.16
Huang et al.18 synthesized F-doped TiO2 using ultra-
sonic spray pyrolysis process.18 The prepared samples
were found to be photocatalytically active under irra-
diation with visible light. The F-doped TiO2 can show
response to visible light by the creation of oxygen vacan-
cies which induced extrinsic absorption, rather than the
substitution nitrogen doping. Generally, a surface photore-
action can be caused by the photoexcitation of both intrin-
sic and extrinsic absorption bands of a photocatalyst.19 20
Fluorinated TiO2 has been often investigated in relation
to doping (TiO2−x Fx
21 22 or surface complexation (F–
TiO2
.23–25 They reported that fluoride doping improves
the crystallinity of anatase and the photocatalytic reactiv-
ity. In addition, TiO2−x Fx has fewer anion vacancies with a
lower density of mid gap states and is more stable against
photocorrosion.
But, non-metal ion doping has some drawbacks, such
as researchers have found that the content of a doped
non-metal component would decrease during the anneal-
ing process thus reducing visible-light photocatalytic
activity.26 Moreover, many studies have demonstrated that
the monodoping elements can act as recombination centers
where photo-induced charges recombine, which reduces
charge quantity and photovoltaic, photocatalytic activity of
TiO2 .27 Therefore, co-doping has been identified as one
of the ways to compensate the drawbacks of single doped
TiO2 . Apart from doping TiO2 with a single metal or non-
metal ion, it is anticipated that doping TiO2 with an appro-
priate combination of metal and non-metal ions would
result in more efficient photocatalysts. On the basis of this,
UV and visible light responsive co-doped photocatalytic
materials have been developed and investigated especially
for environmental remediation purposes. Moreover, these
works have shown that new photocatalyst systems of TiO2
derived by co-doping with a metal and a non-metal dis-
played higher activities for degradation of highly toxic
organic pollutants than that the single metal, non-metal
doped, and pristine TiO2 .
From the mechanistic viewpoint, it turns out that in
metal and nonmetal ion co-doped photocatalyst systems,
Razali et al. Hydrothermal Synthesis and Characterization of Cu2+ /F− Co-Doped Titanium Dioxide (TiO2 ) Nanotubes
the co-doped TiO2 actually reduces the band gap, thus
induces visible light absorption to generate electron–
hole pairs and at same time suppresses the charge-
carrier (electron–hole) recombination process.28 29 Thus
co-doping a metal and a nonmetal has been considered a
good strategy for developing visible light driven photocat-
alyst materials with high photocatalytic activity. Although
various metal and non-metal ion and have been success-
fully doped into TiO2 nanoparticles and mesoporous mate-
rials to promote the photocatalytic activity by changing
the dynamics of electron–hole recombination and inter-
facial charge transfer, no study has been carried out on
synthesizing transition metal ions and non-metal ions co-
doped TiO2 nanotubes in particular Cu2+ and F− doping.
In this paper, novel Cu2+ and F− co-doped TiO2 nano-
tubes were reported regarding to their synthesis method,
physical and chemical properties as well as photocatalytic
activity for methyl orange (MO) degradation. MO has
been widely used in textile industry for dying purpose
and released into ecosystems through wastewater. This dye
is toxic, non-biodegradable and has caused severe envi-
ronmental pollution problems by releasing potential car-
cinogenic substances into the aqueous phase.30 Thus the
degradation of MO aqueous solution is vital for wastew-
ater treatment from textile manufacturing before it can be
safely discharged.
2. EXPERIMENTAL DETAILS
2.1. Preparation of Cu2+ /F− Co-Doped
TiO2 Nanotubes
2.0 grams of the TiO2 powder was mixed with 100 mL
aqueous solution consists of 10 M NaOH, 5.00 mmol
Cu(NO3
2 · 3H2 O and 5.00 mmol NH4 F. The Cu(NO3
2 ·
3H2 O and NH4 F were used as source of copper ion dopant
and fluorine ion co-dopant, respectively. The mixture was
stirred for 30 minutes to obtain a homogeneous solution.
The mixture was subjected to hydrothermal treatment at
150
C for 24 hours in autoclave. After that, the solid
precipitate was collected and washed with 0.1 M HCl
(200 ml) followed by distilled water until the pH 7 of
washing solution was obtained. The final products were
obtained by the filtration with subsequent drying at 80
C
overnight. Subsequently, sample was calcined at 300
C
for 2 hours to produce Cu2+ /F− co-doped TiO2 nanotubes.
Single metal ion doped TiO2 nanotubes and undoped TiO2
nanotubes were synthesized using similar procedure except
the NH4 F was excluded in order to prepare Cu2+ doped
TiO2 nanotubes. Meanwhile, both dopants Cu(NO3
2 ·
3H2 O and NH4 F were excluded to prepare undoped TiO2
nanotubes.
2.2. Characterization
X-ray powder diffraction (XRD) analysis was performed
using a Bruker D8 Diffractometer with Cu-K ( =
154021 Å) and scans were performed in step of
Sci. Adv. Mater., 9, 1–10, 2017
0.2
/second over the range of 2 from 10 to 90
. ZEISS
SUPRATM 35VP field emission scanning electron micro-
scope (FESEM) coupled with EDX and Philips CM12
transmission electron microscope (TEM) was used to
investigate the morphology of the sample. Micromerit-
ics ASAP 2000 instrument was used for the nitrogen gas
adsorption analysis at the temperature of −196
C to deter-
mine the surface area and porosity. The X-ray photoelec-
tron spectroscopy (XPS) spectra of the prepared samples
were attained by means of Kratos Analytical Axis Ultra
DLD photoelectron spectrometer using Al K radiation
monochromatic source.
2.3. Photocatalytic Activity Study
Photocatalytic activity of the samples was studied for
degradation of MO in a photoreactor with 250 ml Pyrex
beaker and opened to air. The photoreactor was set up
inside a closed home-made box. The interior of the box
was lined inner with aluminium foil for reflective interior
surface. The exterior surface of the box was opaque to out-
side light. The photocatalytic degradation experiment was
carried out by adding 0.1 g of prepared samples (Cu2+ /F−
ARTICLE
co-doped, Cu2+ doped and undoped TiO2 nanotubes) into
100 ml of 20 ppm MO dye solution. Prior to photocat-
alytic degradation, aliquot of 5 ml of dye sample was with-
drawn without the presence of any samples and recorded
as blank. Mixtures of TiO2 powder with MO solution were
then put in a reactor and exposed under illumination of
UV bench lamp (302 nm, 230 V ∼50 Hz) for 3 hours. The
aqueous solution was magnetically stirred throughout the
experiment. At every 30 minutes of time intervals, 5 ml of
MO solution was taken out using syringe and then filtered
through 0.45 m millipore syringe filter. Solution was sub-
sequently transferred to a square cuvette and consequently
placed in the sample holder of UV-Vis spectrophotometer.
Then absorption spectra were recorded via UV-Vis spec-
trophotometer (Perkin Elmer Lambda 35 UV-Vis) and the
percentage of MO degradation was calculated using the
formula in Eq. (1);
C0 − Ct
Degradation %
= × 100 (1)
C0
Where C0 is the initial absorption of dye and Ct is the
absorption of dye after the reaction at t time.
3. RESULTS AND DISCUSSION
Figure 1 displays the XRD patterns of Cu2+ /F− co-doped
TiO2 nanotubes as well as Cu2+ doped TiO2 nanotubes
and undoped TiO2 nanotubes for comparison. Undoped
TiO2 nanotubes sample was present as anatase TiO2 phase
(tetragonal) recognized by the peaks appeared at 2 =
∼25.25
, 37.52
, 48.02
, 53.58
, 54.88
, 62.61
, 68.65
,
70.22
, 75.07
and 82.71
(Fig. 1(a)). Meanwhile, Cu2+ /F−
co-doped TiO2 nanotubes sample exhibited three broad
bands at 2 about 19.91
, 23.60
and 48.05
. Cu2+ doped
3
 Hydrothermal Synthesis and Characterization of Cu2+ /F− Co-Doped Titanium Dioxide (TiO2 ) Nanotubes
Fig. 1. XRD patterns of (a) undoped TiO2 nanotubes; (b) Cu2+ doped
TiO2 nanotubes and (c) Cu2+ /F− co-doped TiO2 nanotubes.
TiO2 nanotubes also shows similar XRD pattern and posi-
tions (Figs. 1(b and c)). These bands can be assigned
to TiO2 hexagonal (PDF: 98-005-5018). There are no
other peaks assigned to copper (dopant) or fluorine (co-
ARTICLE
dopant) related phase structure was observed in the XRD
pattern. The absence of copper related phase structure
because the copper element was incorporated into intersti-
tial positions of the lattice TiO2 . Similarly, no diffraction
peaks of fluorine containing phases were recorded for the
co-doped sample, indicating that the fluorine was highly
dispersed into TiO2 and substituted with O in the TiO2
lattice to formed TiO2−x Fx solid solution. This finding is
in good agreement with reports on F doped TiO2 by other
researchers.31 32 Previously, Tosoni et al.,33 reported that
the F− substitution with O would be thermodynamically
favored, while the possibility of F to occupy the intersti-
tial site of the anatase lattice was unfavorable.33 Moreover,
due to the smaller radius of F ions (0.133 nm) compared
to those of O ions (0.140 nm),34 thus the F substitution
was promoted. Yang et al.35 and Yu et al.36 also reported
that fluorine ions easily doped into TiO2 lattice due to the
similarity of fluorine and oxygen ionic radius.35 36
Literature reports two types of doping modes in
oxides which; the interstitial and the substitutional modes,
regardless the type of dopant either metal ion or non-metal
ion.37 38 Doping through the substitutional mode involves
Table I. Lattice parameters, unit cell volume and phase content of undoped TiO2 nanotubes, Cu2+ doped TiO2 nanotubes and Cu2+ /F− co-doped TiO2
nanotubes.
Samples a = b (Å) c (Å)
Undoped TiO2 nanotubes 3781 9509
Cu2+ doped TiO2 nanotubes 526 648
Cu2+ /F− co-doped TiO2 nanotubes 527 645
Anatase TiO2 (tetragonal) 3784 9519
TiO2 hexagonal 529 613
Note: a, b, c = Lattice parameters of unit cell.
4 Sci. Adv. Mater., 9, 1–10, 2017
Razali et al.
the direct substitution of the lattice ions by the dopants.
For metal ions dopant they can substitute titanium, while
for non-metal ions dopant they replace oxygen, conse-
quently occupying their positions into the lattice to form
substitutional solid solutions. This would be favored if the
size of the dopant ions is smaller than titanium or oxygen
ion respectively. On the other hand, if the ionic radius of
dopant is larger than the lattice ions size, an interstitial
doping mode is preferred. In this case, the dopant metal
ions enter into the crystal cell of the oxide. If doping
occurred in this mode, it would lead to significant distor-
tion of the lattice and affect the cell volume largely.
Based on the data in Table I, it was found that the lat-
tice parameter and cell volume of the Cu2+ doped TiO2
nanotubes were significantly different from the undoped
TiO2 nanotubes and it was attributed to the incorporation
of copper into interstitial TiO2 lattice sites. On the other
hand the lattice parameters and cell volume of Cu2+ /F−
co-doped TiO2 nanotubes samples were observed to be
similar to that of Cu2+ doped TiO2 . Therefore, the dop-
ing of F through the interstitial mode could be excluded.
Thus, it is reasonable to suppose that the F ion was doped
into TiO2 by substituting with the O2 in TiO2 lattice. As
compared to copper elements, the copper doped into TiO2
nanotubes by incorporating at interstitial TiO2 lattice sites.
It is interesting also to note that doping and codoping
result in the formation of 100% hexagonal TiO2 , while ear-
lier formation of undoped TiO2 nanotubes was in anatase
form (tetragonal).
The morphology of the undoped, doped and co-doped
TiO2 nanotubes was studied using FESEM and TEM.
Figure 2 shows the FESEM micrographs of Cu2+ /F- co-
doped TiO2 nanotubes as well as Cu2+ doped TiO2 nano-
tubes and undoped TiO2 nanotubes. In particular, all the
samples displayed fibrous-like structures with the diame-
ter around 10 nm and their length was found to be several
hundred nanometers. The presence of the copper as well
as fluorine elements as dopant and co-dopant respectively
is shown in EDX spectra. On top of that, their composition
in the TiO2 matrix is also presented in EDX analysis.
As shown in Figure 3, the TEM images indicate that
the undoped TiO2 nanotubes as well as Cu2+ doped
and Cu2+ /F− co-doped TiO2 nanotubes sample had pre-
dominantly nanotube structures, which were connected
c/a Unit cell volume (Å3 ) Phase Content (wt%)
25149 13802 Anatase TiO2 (tetragonal) 100
12319 16846 TiO2 hexagonal 100
12239 16822 TiO2 hexagonal 100
25145 13624 PDF: 98-000-5225
11588 14869 PDF: 98-005-5018
Razali et al. Hydrothermal Synthesis and Characterization of Cu2+ /F− Co-Doped Titanium Dioxide (TiO2 ) Nanotubes
Fig. 2. FESEM micrographs of (a) undoped TiO2 nanotubes;
(b) 5.00 mmol Cu2+ doped TiO2 nanotubes and (c) 5.00 mmol (Cu2+ /F− )
co-doped TiO2 nanotubes.
randomly in the tube arrangement. The average diameters
of the nanotubes samples were about 10 nm and 4 nm cor-
responding to outer and inner diameters respectively. On
the other hand, the average of the nanotubular structures
lengths ranged from several hundred nanometers. Based
on the TEM images, it can be said that, the presence of
metal ion dopant (Cu2+ ) and non-metal ion co-dopant (F− )
did not change the morphology of the sample because the
dopants were highly dispersed in TiO2 matrix instead of
deposited inside or outside on nanotubes wall.
The elemental analysis of Cu2+ /F− co-doped TiO2 nano-
tubes were performed using EDX. The EDX spectrum
Sci. Adv. Mater., 9, 1–10, 2017
ARTICLE
Fig. 3. TEM micrographs of (a) undoped TiO2 nanotubes; (b) Cu2+
doped TiO2 nanotubes and (c) Cu2+ /F− co-doped TiO2 nanotubes.
in Figure 4(c) displays the presence of fluorine, copper,
titanium and oxygen elements, thus, confirming the pres-
ence of metal ion and non-metal ion of copper and flu-
orine dopants respectively in TiO2 matrix. The detailed
elemental composition is tabulated in Table II. For com-
parison, the EDX spectra of Cu2+ doped TiO2 nanotubes
and undoped TiO2 nanotubes were also included as in
Figures 4(b) and (a), respectively.
Nitrogen gas adsorption–desorption isotherms plot of
the undoped TiO2 nanotubes, Cu2+ doped TiO2 nanotubes
5
 Hydrothermal Synthesis and Characterization of Cu2+ /F− Co-Doped Titanium Dioxide (TiO2 ) Nanotubes Razali et al.

Table II. Average elemental chemical compositions presence in the

samples obtained from EDX spectra.

Samples Ti (at%) O (at%) Cu (at%) F (at%) Total (%)

Undoped TiO2 3329 6671 – – 100

nanotubes
Cu2+ doped TiO2 2811 5622 1567 – 100
nanotubes
Cu2+ /F− co-doped 2766 5533 1564 137 100
TiO2 nanotubes

due to their tubular morphology. Cu2+ doped and Cu2+ /F−

co-doped TiO2 nanotubes samples possess higher surface
area than undoped TiO2 nanotubes, with co-doped having
slightly larger surface area. This may be attributed to the
presence of dopants which could prevent the nanotubes
aggregation and crystallite size growth, thus disfavoring
the formation of larger TiO2 crystallites. It was also sup-
ported by their smaller pore diameter and larger pore vol-
ume compared to undoped mesoporous TiO2 nanotubes. In
other words the doped and co-doped TiO2 nanotubes sam-
ples carried more number of pores per gram than undoped
ARTICLE

TiO2 nanotubes. Large surface area and high pore vol-

ume of those samples provide abundant active sites for
adsorption–oxidation reaction and increase the photocat-
alytic degradation capacity respectively.
The XPS survey spectrum of Cu2+ /F− co-doped TiO2
nanotubes in Figure 8, indicates the peaks related to tita-
nium, oxygen, copper, fluorine and carbon elements. Tita-
nium, oxygen, copper, and fluorine elements are belong
to the studied sample. On the other hand, the presence of
carbon (C) element was ascribed to adventitious carbon
contamination species from XPS measurement.39
Figure 9 shows the high resolution XPS spectra of Ti 2p
over the Cu2+ /F− co-doped TiO2 nanotubes. An unsym-
metrical peak was observed, which means that there exist
two chemical forms of Ti in the sample. Two strong peaks
located at 457.1 and 462.8 eV binding energies were

Fig. 4. EDX spectra of (a) undoped TiO2 nanotubes; (b) Cu2+ doped
1000
TiO2 nanotubes and (c) Cu2+ /F− co-doped TiO2 nanotubes.

800
and Cu2+ /F− co-doped TiO2 nanotubes were depicted in
Figures 5–7. All the isotherms showed similar features
Volume (cm3/g)

with the existence of hysteresis loop at high relative pres- 600

sure. The features corresponded to the isotherm type IV,

desorption

evidencing the presence of the mesopores in the samples 400

adsorption

as tabulated in Table III. All studied samples also exhibits

similar shape of pores which is the slit shaped pores 200
attributed to their H3 types of hysteresis (Table III). The
results obtained were in good agreement with the TEM
0
images which showed the uniform nanotubular structures. 0.0 0.2 0.4 0.6 0.8 1.0
Table IV presents the specific surface area, pore volume Relative pressure, P/Po
and pore diameter of the samples. The mesoporous TiO2
nanotubes samples showed high surface area (>200 m2 /g), Fig. 5. Isotherm plot of undoped TiO2 nanotubes.

6 Sci. Adv. Mater., 9, 1–10, 2017

Razali et al. Hydrothermal Synthesis and Characterization of Cu2+ /F− Co-Doped Titanium Dioxide (TiO2 ) Nanotubes

1200 Table III. Type of isotherms, hysteresis, pores and shape of pores for
various TiO2 nanotubes samples.
1000
Type of Type of Type of Shape of
Samples isotherms hysteresis pores pores
Volume (cm3/g)

800
Undoped TiO2 IV H3 Mesopore Slit shaped
600 nanotubes pores

adsorption
Cu2+ doped TiO2 IV H3 Mesopore Slit shaped

desorption
nanotubes pores
400
Cu2+ /F− co-doped IV H3 Mesopore Slit shaped
TiO2 nanotubes pores
200

0
0.0 0.2 0.4 0.6 0.8 1.0 binding energy could be identified. The peak appeared at
Relative pressure, P/Po 530.2 eV was attributed to the hydroxyl surface species
of [O–H].46–48 The binding energy position of O 1s peaks
Fig. 6. Isotherm plot of Cu2+ doped TiO2 nanotubes. for (Cu2+ /F− ) co-doped TiO2 nanotubes shifted to lower
value as compared to the undoped TiO2 nanotubes. This
attributed to the Ti4+ 2p1/2 and Ti4+ 2p3/2 spin-orbital is attributed to the influence of fluorine ions substituted
splitting photoelectrons respectively, showing the presence oxygen in the TiO2 lattice, since fluorine ion radii are com-
of Ti4+ . This is in good agreement with the values reported parable with those of the oxygen.
in literatures.40–42 Using PeakFit program, besides the pre- Figure 11 displays the high resolution XPS spectra of
dominant Ti4+ peaks observed at 457.1 and 462.8 eV, a Cu 2p of 5.00 mmol (Cu2+ /F− ) co-doped TiO2 nanotubes.
minor species of titanium was also found located at 456.0 Two peaks were centered at 931.4 and 951.3 eV bind-

ARTICLE
and 461.7 eV binding energies. These could be identified ing energies were observed. These peaks were assigned to
as Ti3+ 2p3/2 and Ti3+ 2p1/2 , respectively suggesting the Cu 2p3/2 and Cu 2p1/2 respectively and characteristics for
presence of Ti3+ species in the co-doped TiO2 nanotubes Cu+ .49 The presence of Cu+ species was due to the reduc-
sample. tion of Cu2+ to Cu+ during XPS measurements, when the
The formation of Ti3+ was attributed to the charge Cu content was low and existed in a highly dispersed in
imbalance because of O substitution by F ions in the TiO2 the TiO2 .
lattice after F doping. Yu et al.43 and Zhao et al.44 also The high resolution XPS spectra of F 1s of Cu2+ /F− co-
found the existence of Ti3+ after F was doped into TiO2 doped TiO2 nanotubes are shown in Figure 12. The F 1s
due to their charge compensation (excess electron in the region was composed of one major peak located at 688 eV.
lattice) thus resulting in reduction of Ti4+ to Ti3+ .43 44 Yu et al.50 reported the F 1s binding energy at around
As shown in Figure 10, after deconvolution the O 1s 688 eV is ascribed to the F− ions in the TiO2 lattice,
high resolution XPS spectra of co-doped TiO2 nanotubes while the peak at lower binding energy (∼684 eV), cor-
consist of two peaks. Besides the main peak of O 1s responded to the adsorbed F− ions on the TiO2 surface.50
located at about 528.6 eV corresponding to lattice oxygen Therefore, it can be concluded the fluorine co-dopant was
of TiO2 [O–Ti],45 another one shoulder peaks at higher incorporated into TiO2 by replacing and occupied the oxy-
gen site in the TiO2 crystal lattice to form solid solu-
1200 tion of TiO2−x Fx . Although the intensity of the F 1s
weak, one major peak ascribed to the F− ion in the
1000 lattice exhibits strong evidence of F− ion was incorpo-
rated into TiO2 crystals. In addition, no peak located at
800
∼684 eV was observed, suggesting the absence of the
Volume (cm3/g)

600 Table IV. Surface area, pore size and pore volume of undoped TiO2
nanotubes, Cu2+ doped and Cu2+ /F− co-doped TiO2 nanotubes samples.
desorption

400 Samples Surface area Pore size Pore volume

adsorption

(m2 /g) (nm) (cm3 /g)

200
Undoped TiO2 226521 4688 0374
nanotubes
0 Cu2+ doped TiO2 274982 4465 0521
0.0 0.2 0.4 0.6 0.8 1.0 nanotubes
Relative pressure, P/Po Cu2+ /F− co-doped 288448 4421 0546
TiO2 nanotubes
Fig. 7. Isotherm plot of Cu2+ /F− codoped TiO2 nanotubes.

Sci. Adv. Mater., 9, 1–10, 2017 7

 Hydrothermal Synthesis and Characterization of Cu2+ /F− Co-Doped Titanium Dioxide (TiO2 ) Nanotubes
O 1s
Intensity (arb. units)
OKLL
Ti 2p
Cu 2p
Ti 2s
F 1s
1000 900 800 700 600 500
Bindings Energy (eV)
Fig. 8. XPS spectra of Cu2+ /F− co-doped TiO2 nanotubes.
physically absorbed F species on the co-doped TiO2 nano-
tubes surface. Furthermore, calcination at high tempera-
ture (300
C) in preparing co-doped TiO2 nanotubes could
remove the adsorbed F species from the TiO2 nanotubes
surface.51 52
Figure 13 shows the photocatalytic degradation of MO
using of Cu2+ /F− co-doped TiO2 nanotubes and Cu2+
doped TiO2 nanotubes as well as undoped TiO2 nano-
ARTICLE
tubes. It can be observed that the Cu2+ /F− co-doped TiO2
nanotubes demonstrated better MO photodegradation as
compared to single Cu2+ doped and much higher photo-
catalytic performance than undoped TiO2 nanotubes. This
indicates the synergistic effects of doped and codoping of
the TiO2 nanotubes. Higher photocatalytic activity of Cu2+
doped TiO2 nanotubes sample for MO degradation as com-
pared to undoped TiO2 nanotubes was attributed to the
present of Cu2+ doping which could prevent the crystal-
lite size growth and nanotubes agglomeration to produce
doped TiO2 nanotubes with higher surface area. The cop-
per ion dopant also acts as electron and hole traps, which
is can restrain the recombination rate of photogenerated
electrons and holes. On top of that, intercalation of copper
dopant into TiO2 reduces the band gap energy,53 allowed
Fig. 9. High resolution XPS spectra of Ti 2p of Cu2+ /F− co-doped TiO2
nanotubes; XPS analysis peak (solid line) and deconvolution peak (hol-
low line).
8 Sci. Adv. Mater., 9, 1–10, 2017
Razali et al.
C1s
400 300 200 100 0
Fig. 10. High resolution XPS spectra of O 1s of Cu2+ /F− co-doped
TiO2 nanotubes; XPS analysis peak (solid line) and deconvolution peak
(doted line).
a broad range of hv absorption to generate more electron
and hole thus resulting in rapid degradation of MO dye.
On the other hand, improved degradation reactivity of
Cu2+ /F− co-doped TiO2 nanotubes as compared to Cu2+
doped TiO2 nanotubes and undoped TiO2 nanotubes was
due to the synergic effect of copper and fluorine ion co-
dopants. Besides the effects of copper dopant which could
enhanced the photocatalytic activity, the addition of flu-
orine as co-dopant increases further the performance of
co-doped TiO2 nanotubes by producing more active sites
for photocatalytic degradation reaction with the forma-
tion of Ti3+ after F codoping.54 55 Interestingly, the exis-
tence of Ti3+ surface state can act as the electron trapper
thus prevent the recombination of electron (e− ) with pos-
itive holes (h+ ).56 The trapped electron was then reacted
with the adsorbed O2 on the surface of TiO2 , resulted in
increasing of superoxide ions radicals ( O− 2 ) formation.
The radicals plays an important roles in degrading MO
thus supported good photocatalytic activity of Cu2+ /F− co-
doped TiO2 nanotubes.The formation of Ti3+ was observed
and reported in XPS analysis. Li et al.54 also reported that,
as a result of the high electronegativity of fluorine, the flu-
orination of TiO2 increased the surface acidity, which is
Fig. 11. High resolution XPS spectra of Cu 2p of Cu2+ /F− co-doped
TiO2 nanotubes.
Razali et al. Hydrothermal Synthesis and Characterization of Cu2+ /F− Co-Doped Titanium Dioxide (TiO2 ) Nanotubes
Fig. 12. High resolution XPS spectra of F 1s of Cu2+ /F− co-doped TiO2
nanotubes.
important for adsorption of organic pollutant like MO.52
As known, the degradation of MO was initiated by adsorp-
tion of MO on the surface the photocatalyst.57 This conse-
quently affects the interfacial charge transfer rate and thus
the photocatalytic reaction.
Moreover, a new pathways for  OH radicals formation
in aqueous solution was observed with the present of F
as dopant.58 The F co-doped promotes the production of
mobile free OH radicals ( OHfree ) by oxidizing adsorbed
H2 O (H2 Oads ) as in Eq. (2), whereas most OH radicals gen-
erated on undoped TiO2 surface prefer to remain adsorbed
( OHads ) as shown in Eq. (3):
Ti − F + H2 Oads or OH−
+ h+
VB
→ Ti − F + OHfree + H+
Ti − OH + h+
VB → Ti − 
OH+
ads
The formation of  OHfree is important because they can
move freely to speed up the MO degradation reaction to
yield the degraded products. The synergistic action by the
Fig. 13. Photocatalytic degradation of MO using Cu2+ /F− co-doped
TiO2 nanotubes, Cu2+ doped TiO2 nanotubes and undoped TiO2
nanotubes.
Sci. Adv. Mater., 9, 1–10, 2017
Cu2+ and F− ions co-doping leads to the improved reac-
tivity of metal ion/non-metal ion co-doped TiO2 nanotubes
for photodegradation of MO dye.
4. CONCLUSIONS
Cu2+ /F− co-doped TiO2 nanotubes was were successfully
synthesized via hydrothermal method. Based on the results
and analysis, it can be concluded that the addition of non-
metal ion of F as co-dopant did not significantly change
the nanotubular morphology, and the band gap energy as
well as TiO2 hexagonal phase structure of Cu2+ /F− co-
doped TiO2 nanotubes when compared to single metal
ion of Cu2+ doped TiO2 nanotubes. Nevertheless, their
surface area and pore volume were found to be larger
than Cu2+ doped TiO2 nanotube and undoped TiO2 nano-
tubes. These resulted in higher photocatalytic activity of
Cu2+ /F− co-doped TiO2 nanotubes. Moreover, the pres-
ence of F codoping contributed to the Ti3+ formations,
which apparently would enhanced the photocatalytic activ-
ity. The formation of  OH is also favored on Cu2+ /F− co-
doped TiO2 nanotubes, whereby F codoping creates new
active sites for  OH free generation. On top of that, surface
ARTICLE
acidity of Cu2+ /F− co-doped TiO2 nanotubes promote the
adsorption of MO for photocatalytic degradation. These
effects (Ti3+ formation, surface acidity and  OH new path-
way) ultimately resulted in increasing photocatalytic activ-
ity of Cu2+ /F− co-doped TiO2 nanotubes for degradation
of MO.
Acknowledgments: The authors are grateful to Uni-
versiti Malaysia Terengganu (UMT) for providing the
facilities to carry out this project and Ministry of Higher
Education of Malaysia for the financial support vote FRGS
(2) 59358.
(3)
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