Co2+ Addition Effect on the Photocatalytic Activity of TiO2 Nanorod Thin Films

zge Kerkez,1* smail Boz 2

1

Chemical Engineering Department, Beykent University, stanbul 34396, Turkey

Chemical Engineering Department, stanbul University, stanbul 34320, Turkey

Abstract TiO 2 nanorod array thin films were synthesized by a hydrothermal method and then modified with an ultrasonicassisted sequential cation adsorption method with Co2+. The samples were characterised by XRD, UVvis DRS, SEM, ICPMS analysis. Photocatalytic activities were tested by methylene blue degradation under visible light. Methylene blue
degradation efficiency under visible light was increased 29% with respect to the efficiency of the pure TiO 2/FTO sample.

TiO2 is the most suitable photocatalyst in terms of

stability, resistance, being harmless to the environment. TiO 2
has a disadvantage that it only can be excited under UV
illumination. Various studies have been reported such as noble
metal/transition metal/anions doping to increase its absorption
in the visible light range to utilize the sunlight. On the other
hand, it was determined that the 1D nanostructures of TiO 2
have shown superior performance than conventional thin films
in photocatalytic processes [1,2]. In this context, the aim of
this study to increase the absorbance in the visible light by
Co2+ adding and the activity by synthesizing TiO2 in nanorod
shape.
TiO2 Nanorod thin film (TiO2/FTO) was prepared by the
hydrothermal method [3]. Co2+ adding was performed by
ultrasonic assisted sequential cation adsorption method [4].
Five different concentrations (0.01; 0.025; 0.050; 0.075;
0.100M) of aqueous Co(NO3)26H2O solutions were used to
see the effect of Co2+ amount. The samples were named as
10Co2+-TiO2/FTO according to the initial metal concentration.
Methylene blue photodegradation reactions were done in a
home made reaction chamber with a 105-W energy saver
white fluorescent (main emission wavelength 530 nm). The
experiments were carried out in a quartz cell (1cm x 1cm x
4cm) filled with 3 ml, 5 ppm methylene blue solution.

energy has decreased as the Co2+ amount increased on the

film. That indicates the photocatalyst film has became more
sensitive to the visible light. ICP-MS analysis was conducted
to determine the Co2+ amount on the film; results are given in
Table I. Figure 4 represents the kinetic behaviour of MB
photodegradation. LangmuirHinshelwood rate expression has
been fitted well with the relationship between the initial
degradation rate and the concentration of the organic dye for
heterogeneous photocatalytic processes occurring at the solid
liquid interface [5,6]. Degradation% values and apparent
reaction rate constants (k) are summarized in Table I.
TiO2/FTO obtained 47.2% conversion of methylene blue by
the self-sensitised degradation. Methylene blue degradation
was increased under visible light through Co2+ addition. The
maximum dye degradation efficiency was achieved with
50Co2+-TiO2/FTO. Degradation efficiency under visible light
was increased 29% with respect to the efficiency of the pure
TiO2/FTO sample. The maximum reaction rate constant was
found as 3.8x10-3 min-1 with 50Co2+-TiO 2/FTO.

Figure-3: UV-vis absorption spectra

of the samples

Figure-4: Reaction kinetics of MB

degradation

Table-I Some properties of photocatalyst samples, MB degradation% and

reaction rate constants
Figure-1: SEM photo of
TiO2/FTO sample

Figure-2: XRD pattern of

Co2+-TiO2/FTO samples

Figure 1 represents the SEM photo of TiO2/FTO sample. The

image reveal that the surface of the substrate uniformly
covered with TiO2 nanorods. Figure 2 represents the XRD
pattern of the Co2+ modified TiO2 nanorod thin films. It is
supported the rutile phase of TiO 2 (JCPDS No. 88-1175) is
synthesized successfully in nanorod shape understood from
the (002) (2h = 62.77) diffraction peak. No separate Co/Co2+
phases were observed because of low concentration. Figure 3
represents the UV-vis absorption spectra of the samples. The
UV-vis spectra of the pure TiO 2/FTO show very low
absorption in the visible light region, while Co2+TiO2/FTO
films exhibit higher absorption in the visible light. The direct
band gap energy of the samples were calculated and given in
Table I. Visible light absorption has increased and band gap

*Corresponding author: okerkez@gmail.com

[1] J.-H. Yoon et al., Journal of Photochemistry and Photobiology A:
Chemistry 180, 184 (2006).
[2] X.D. Li et al., Materials Chemistry and Physics 124, 179 (2010).
[3] B. Liu et al., Journal of American Chemical Society 131, 3985 (2009).
[4] . Kerkez et al., Journal of Physics and Chemistry of Solids 75, 611
(2014).
[5] Y.-H.Xu et al., Materials Research Bulletin 43, 3474 (2008).
[6] K. Naeem et al., Physica B 405, 221 (2010).