Effects of Single and Double Doping with Ni and Pt on the

Photo(electro)catalytic Activity of TiO2 Nanorod Films

2+

zge Kerkez , smail Boz

1,2

Beykent University, Engineering and Architecture Faculty, Chemical Engineering, 34396, stanbul, Turkey
2
stanbul University, Engineering Faculty, Chemical Engineering, 34320, stanbul, Turkey
ABSTRACT

TiO2, Ni2+-TiO2, Pt0-TiO2 and Pt0-Ni2+-TiO2 nanorod films were prepared on transparent conducting oxide glass (FTO/F:SnO 2). The samples were characterised by XRD, UVvis DRS, SEM, PL
spectroscopy. The photoelectrochemical properties of the samples were evaluated by linear sweep voltammetry, photocatalytic activities were tested by methylene blue degradation under visible light.
Pt0-Ni2+-TiO2/FTO showed superior photoelectrocatalytic activity with 1.358 mA cm -2 and 78.3% methylene blue degradation under visible light. Quantum yields were calculated separately as a sign for
H2 generation rate and as a conversion of methylene blue molecule per absorbed light.

MOTIVATION AND INTRODUCTION

TiO2 nanorod arrays have low e--h+ recombination rate compared to TiO2 thin film systems.
So, their photocatalytic activities are expected to higher than the conventional thin films.
Transition metal modified TiO2 shows superior photo(electro)catalytic activity under visible
light. Thus we would like to investigate the combined effect of 1D shape of TiO2 and
modification with transition metal.
The motivation of this study is to investigate the synergistic effect of these Ni2+ cation with
Pt0 on the photo(electro)catalytic activity of TiO2 nanorod thin films prepared by the
ultrasonic-assisted sequential cation adsorption method with expecting high
photo(electro)catalytic activity.

1D nanostructured TiO2 photoelectrodes obtain retarded recombination of e --h+ pair, the oriented
structure gives more chance to e- to participate the surface reactions so the
photo(electro)catalytic activity increases.
Hydrothermal method is a controllable method that the final film properties can be changed by
adjusting the reaction conditions.
Unfortunately TiO2 has a disadvantage of very low absorbance in visible light. The recent studies
also have consisted the increase the solar absorption of TiO 2 by doping transition metals (Fe3+,
Cu2+, Cr2+) [1,2]. These modifications of TiO2 affect the photo(electro)catalytic activity under
visible light via different mechanisms such as forming impurity energy levels in band positions or
being a composite with a lower band gap semiconductor [3].

EXPERIMENTAL

Photocatalytic Reactions

Sample Preparation
FTO glass (1 cm x 2 cm) cleaning procedure

5 ppm, 3 ml methylene blue aq.

Solution
1 cm x 1 cm x 4 cm quartz
reaction vessel
45 min adsorption-desorption eq.
in dark
105 W energy saver white
fluorescent lamp with the main
emission wavelength 530 nm.
MB conc. was followed by UV-vis
Spectrometer at 665 nm.

HCl:H2O solution (1:1)

TiCl4 addition (1.0 ml)
Hydrothermal reaction,
presence of FTO in the autoclave (180C, 2h)
Ni2+ adding was performed by ultrasonic assisted sequential cation
adsorption method. 0.050 M aqueous Ni2+ solution was used.
Pt loading was performed as second step. The same ultrasonic
assisted adsorption method was used. 0.010 M H 2PtCl6 aqueous
solution. After the samples were dried, they were kept under UV
illumination for 2 hours to reduce Pt4+ to Pt0.
TO
F
/
TiO 2
SEM

RESULTS

XRD

2+

Pt -Ni -TiO2/FTO

1.5

UV-vis DRS

TiO2/FTO

2+

Pt -TiO2/FTO

Ni -TiO2/FTO
0

Pt -TiO2/FTO

TiO2/FTO

TiO2/FTO

Pt -TiO2/FTO
0

2+

Pt -Ni -TiO 2/FTO

2+

Pt -Ni -TiO2/FTO

Ni -TiO2/FTO

[hvf(R)]

Absorbance

2+

Ni -TiO2/FTO

2+

1.0

(hv)1/n = A(hv-Eg)
(hvf(R))1/n = A(hv-Eg)

0.5

FTO
0.0

20

30

40

50

60

400

70

600

400

450

500

Photocurrent
density @1V
(A/cm2)

0
0

550

600

400

500

Quantum Degredation
yield for H2 efficiency for
MB %
production
(%)*

2+

I-V curves

0.4
0.2
0.0

3.09

3.58

0.001

47.2

3.0

0.0027

Ni2+-TiO2/FTO

2.45

2.88

135.60

0.039

77.4

5.8

0.0052

Pt0-TiO2/FTO

2.66

3.05

70.78

0.020

80.5

7.1

0.0063

Pt0-Ni2+-TiO2/FTO

2.36

2.97

1358.00

0.386

78.3

6.6

0.0059

0.10

0.00

CONCLUSION

-0.05

-0.4

-0.2

0.0

0.2

0.4

0.6

0.8

1.0

Quantum
yield for MB
degredation
(%)**

2.60

0.15

0.05

Reaction
rate
constant
kappx10-3
(min-1)

TiO2/FTO
2

0.6

600

Wavelength (nm)

Pt -Ni -TiO2/FTO

0.8

-0.2
-0.6

Pt -TiO2/FTO

Wavelength (nm)

Pt -TiO2/FTO

1.0

TiO2/FTO

PL

Photocatalyst film Crystallite Band

sample
size (nm) gap
(eV)

Photocurrent density (mA/cm )

P hotocurrent density (mA/cm )

Peak 1 (3,13 eV)

Peak 2 (3,00 eV)
Peak 3 (2,73 eV)
Peak 4 (2,63 eV)
Peak 5 (2,55 eV)

**

2+

Ni /TiO2/FTO

TiO2/FTO

1.4
1.2

3.25

hv (eV)

Rutile phase of TiO2 (JCPDS No. 88-1175) is synthesized successfully in nanorod shape understood from the
(002) (2h = 62.77) diffraction peak. No separate Ni/Ni 2+ or Pt phases were observed because of low
concentration.

TiO 2/FTO

3.00

Wavelength (nm)

2theta (degree)

1000 W Xe lamp. The irradiance was

measured to be 810 W/m2. the nanorod
array thin film as the working electrode (1.0
cm2 area), Ag/AgCl in a KCl-saturated
solution as the reference electrode and
platinum plate as the counter electrode. 0.5
M Na2SO4 solution was used as electrolyte.

2.75

800

1.2

Potential (V vs. Ag/AgCl)

-0.6

-0.4

-0.2

0.0

0.2

0.4

0.6

0.8

1.0

1.2

Potential (V vs. Ag/AgCl)

REFERENCES
[1] S. Xu, A. J. Du, J. Liu, J. Ng, D. D. Sun, Highly efficient CuO incorporated TiO2 nanotube photocatalyst for hydrogen production from water,
Int. J. Hydrogen Energ. 36 (2011) 6560-6568.
[2] H. Zhu, J. Tao, X. Dong, Preparation and Photoelectrochemical Activity of Cr-Doped TiO2 Nanorods with Nanocavities, J. Phys. Chem. C 114
(2010) 28732879.
[3] L. Sun, J. Li, C.L.Wang, S.F. Li, H.B. Chen, C.J. Lin, An electrochemical strategy of doping Fe3+ into TiO2 nanotube array films for
enhancement in photocatalytic activity, Sol. Energ. Mat. Sol. C. 93 (2009) 18751880.
[4] Chatterjee, D., Dasgupta, S., Visible light induced photocatalytic degradation of organic pollutants, J. Photoch. Photobio. C 6 (2005) 186
205.

Enhanced photo(electro)chemical properties was achieved with Pt 0-Ni2+-TiO2/FTO with synergistic effect
of e- trap feature of Pt0 and band gap narrowing of Ni2+.
% is the efficiency of photon to hydrogen generation, the maximum efficiency was achieved by Pt0-Ni2+TiO2/FTO as 0.386%.
Methylene blue conversion achieved by pure TiO 2/FTO (47.2%) was based on a self-sensitized
degradation process of coloured contaminant for the irradiation between 400-800 nm [4]. Ni 2+-TiO2/FTO
showed 77.4% degradation this is attributed to the low band gap value 2.88 eV.
Pt0-TiO2/FTO showed 80.5% degradation owing to self-sensitized degradation and e --h+ recombination
retarding effect of Pt0.