Professional Documents
Culture Documents
An electrochemical strategy of doping Fe3+ into TiO2 nanotube array lms for
enhancement in photocatalytic activity
L. Sun a,, J. Li a, C.L. Wang a, S.F. Li a, H.B. Chen a, C.J. Lin a,b,
a
b
Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China
State Key Laboratory for Physical Chemistry of Solid Surfaces, Xiamen University, Xiamen 361005, China
a r t i c l e in fo
abstract
Article history:
Received 12 June 2008
Received in revised form
25 June 2009
Accepted 1 July 2009
Available online 19 July 2009
Highly ordered Fe3+-doped TiO2 nanotube array lms were fabricated directly by the electrochemical
anodic oxidation of pure titanium in an HF electrolyte solution containing iron ions. The morphology,
structure and composition of the as-prepared nanotube array lms were characterized by SEM, Raman
and XPS. The effects of dopant amount on the morphologies, structure, photoelectrochemical property
and photoabsorption of the TiO2 nanotube array lm were investigated. The results showed that Fe3+
was successfully introduced into the nanotube array lm. Compared with the undoped TiO2 nanotube
array lm, the photocurrent of Fe3+-doped TiO2 nanotube array lms increased obviously. The
absorption edge of Fe3+-doped TiO2 nanotube array lms appeared to be red shifted. The photocatalytic
activity of Fe3+-doped TiO2 nanotube array lms was evaluated by the removal of methylene blue (MB)
aqueous solution. A maximum enhancement of photocatalytic activity was achieved for Fe3+-doped TiO2
nanotube array lm prepared in 0.10 M Fe(NO3)3+0.5% HF electrolyte under UV irradiation, which
attributes to the effective separation of photogenerated electronhole upon the substitutional
introduction of appropriate Fe3+ amount into the anatase TiO2 structure.
& 2009 Elsevier B.V. All rights reserved.
Keywords:
Photocatalysis
TiO2 nanotube array lm
Iron doping
Anodic oxidation
Photoelectrochemical property
1. Introduction
Since the synthesis of unique, highly ordered TiO2 nanotube array
lm was reported in 2001 [1], it has been attracting considerable
attention over the past several years in photocatalytic degradation of
pollutants [24], solar cell [57], gas sensor [8,9] and photolysis
water [10,11] applications. However, the relatively large bandgap of
TiO2 (3.2 eV) limits the efciency of photocatalytic reactions due to
the high recombination rate of photogenerated electrons and holes
formed in photocatalytic process and the low absorption capability
for visible light. Many studies have been devoted to the improvement of photocatalytic efciency of TiO2 nanotube array lm, such
as doping metal ions [12] or non-metal [1315] and semiconductor
nanoparticle modication [16].
Comparatively, doping TiO2 with transition metal cations is an
effective strategy to reduce electronhole recombination rate and
increase photocatalytical efciency. In particular, Fe3+ is considered an interesting dopant of TiO2 in terms of its semi-full
electronic conguration and ion radius close to Ti4+. Many efforts
concerning Fe3+-doped TiO2 focus on the topic of nanoparticle
powders or nanoparticle lms, including preparation, character-
2. Experimental
Corresponding author. Tel.: +865922184655; fax: +865922189354.
Corresponding author at: Department of Chemistry, College of Chemistry and
ARTICLE IN PRESS
1876
L. Sun et al. / Solar Energy Materials & Solar Cells 93 (2009) 18751880
2
2
n 1; 2; 3; . . . ; 6
Fe3 nF -FeF3n
n
Fig. 1. SEM images of the undoped TiO2 nanotube array lm (aand b) and Fe3+doped TiO2 nanotube array lms prepared in 0.5% HF electrolyte containing 0.05 M
(c), 0.15 M (d), 0.20 M (e), Fe(NO3)3, respectively.
ARTICLE IN PRESS
L. Sun et al. / Solar Energy Materials & Solar Cells 93 (2009) 18751880
1877
1600000
1400000
Ti LMM
O1s
O KLL
1200000
4
Counts (s)
1000000
Ti2p
Ti2s
Fe2p
800000
600000
2
400000
200000
Ti3p
C1s
O2s
Ti3s
200
400
600
200
400
600
Binding Energy (eV)
800
1000
Time (s)
Fig. 2. Currenttime transients recorded for a titanium electrode at a constant
voltage of 10 V in 0.5% HF solution with and without addition of Fe(NO3)3.
Fe2p3/2(710.1eV)
700
705
710
715
720
Binding Energy (eV)
725
730
Fig. 3. (a) XPS survey spectrum for Fe3+TiO2 nanotube array lm over a large
energy range and (b) Fe 2p XPS core-level spectrum of Fe3+TiO2 nanotube array
lm.
Intensity (a.u.)
Fe2p1/2(723.7eV)
Intensity (a.u.)
3+
(d)
(c)
R
100
A: anaste
R: rutile
(a) TiO2
(b) 0.05 M Fe(NO3)3
(c) 0.10 M Fe(NO3)3
(d) 0.15 M Fe(NO3)3
A
200
300
400
500
600
(b)
(a)
700
800
mainly originates from the Fe3+ dopant into the crystal lattice
of TiO2 because the atom radius of Fe3+ is very close to that of Ti4+,
which results in the structure changes of crystal lattice, leading to
cleavage of the vibration phonon mode.
ARTICLE IN PRESS
1878
L. Sun et al. / Solar Energy Materials & Solar Cells 93 (2009) 18751880
3000
2500
2000
0.05 M Fe(NO3)3
0.10 M Fe(NO3)3
0.15 M Fe(NO3)3
Absorbance (a.u.)
Photocurrent (nA)
TiO2
TiO2
0.05 M Fe(NO3)3
0.10 M Fe(NO3)3
0.15 M Fe(NO3)3
1500
1000
500
0
250
300
350
400
450
500
Wavelength (nm)
Fig. 5. Photocurrent spectra of the TiO2 nanotube array lm and Fe3+TiO2
nanotube array lms.
300
400
450
500
Wavelength (nm)
550
600
Fig. 6. UVvis spectra of the TiO2 nanotube array lm and Fe3+TiO2 nanotube
array lms.
2.0
photolysis
TiO2
0.05 M Fe(NO3)3
0.10 M Fe(NO3)3
0.15 M Fe(NO3)3
1.6
ln(Co/Ct)
350
1.2
0.8
0.4
0.0
0
20
40
60
Time (min)
80
100
ARTICLE IN PRESS
L. Sun et al. / Solar Energy Materials & Solar Cells 93 (2009) 18751880
1879
E NHE(V)
Table 1
The apparent rst-order rate constant k of photocatalytic degradation of MB for
the TiO2 nanotube array lm and Fe3+TiO2 nanotube array lms.
Nanotube array lm
Correlation
coefcient, R2
TiO2
Fe3+TiO2 (0.05 M
Fe(NO3)3+0.5%HF)
Fe3+TiO2 (0.10 M
Fe(NO3)3+0.5%HF)
Fe3+TiO2 (0.15 M
Fe(NO3)3+0.5%HF)
0.537
0.600
0.997
0.987
0.972
0.558
-1.0
0
1.0
TiO2
e-
CB
e-
Eg=3.2eV
h< Eg
2.0
0.993
3.0
0.996
VB
Fe3+/Fe2+
h+
Fe4+/Fe3+
h+
Fig. 8. Schematic diagram illustrating the charge transfer from excited TiO2 to the
different states of Fe ions. CB and VB refer to the energy levels of the conduction
and valence bands of TiO2, respectively.
TiO2 hn
hvb
4
Fe3 h
vb -Fe
2
Fe3 e
cb -Fe
Fe2 O2 ads-Fe3 O
2
10
11
4. Conclusion
This work demonstrates for the rst time an efcient Fe3+
doping in the highly ordered TiO2 nanotube array lms directly
using electrochemical anodic oxidation. The structure of highly
ordered array remains when the concentration of Fe(NO3)3 in the
anodic electrolyte is lower than 0.15 M. Comparative analysis by
different characterization techniques (XPS, Raman, photocurrent
and UVvis spectrum) indicates that Fe3+ is effectively incorporated into TiO2 lattice. The strong enhancement of the photocurrent and the obvious absorption for TiO2 nanotube arrays are
evidenced to be related to the Fe3+ dopant. The appropriate
amount of doped Fe3+ (ca. 0.10 M Fe(NO3)3) in TiO2 nanotube array
lm plays a crucial role in effectively improving the photocatalytic
activity of photocatalysts under UV irradiation.
Acknowledgments
We gratefully acknowledge the nancial support from the
Natural Science Foundation of Fujian Province, China (U0750015),
Technical Program of Fujian Province, China (2007H0031) and
Technical Program of Xiamen City, Fujian Province, China
(3502Z20073004).
References
[1] D. Gong, C.A. Grimes, O.K. Varghese, W.C. Hu, R.S. Singh, Z. Chen, E.C. Dickey,
Titanium oxide nanotube arrays prepared by anodic oxidation, J. Mater. Res.
16 (12) (2001) 33313334.
[2] J.M. Macak, M. Zlamal, J. Krysa, P. Schmuki, Self-organized TiO2 nanotube
layers as highly efcient photocatalysts, Small 3 (2) (2007) 300304.
[3] Y.K. Lai, L. Sun, Y.C. Chen, H.F. Zhuang, C.J. Lin, J.W. Chin, Effects of the
structure of TiO2 nanotube array on Ti substrate on its photocatalytic activity,
J. Electrochem. Soc. 153 (7) (2006) D123D127.
[4] H.F. Zhuang, C.J. Lin, Y.K. Lai, L. Sun, J. Li, Some critical structure factors of
titanium oxide nanotube array in its photocatalytic activity, Environ. Sci.
Technol. 41 (13) (2007) 47354740.
[5] G.K. Mor, K. Shankar, M. Paulose, O.K. Vargheese, C.A. Grimes, Use of highlyordered TiO2 nanotube arrays in dye-sensitized solar cells, Nano Lett 6 (2)
(2006) 215218.
[6] H. Wang, C.T. Yip, K.Y. Cheung, A.B. Djurisic, M.H. Xie, Y.H. Leung, W.K. Chan,
Titania-nanotube-array-based photovoltaic cells, Appl. Phys. Lett. 89 (2)
(2006) (No.023508).
ARTICLE IN PRESS
1880
L. Sun et al. / Solar Energy Materials & Solar Cells 93 (2009) 18751880
[7] M. Paulose, K. Shankar, O.K. Varghese, G.K. Mor, B. Hardin, C.A. Grimes,
Backside illuminated dye-sensitized solar cells based on titania nanotube
array electrodes, Nanotechnology 17 (5) (2006) 14461448.
[8] O.K. Varghese, D.W. Gong, M. Paulose, K.G. Ong, E.C. Dickey, C.A. Grimes,
Extreme changes in the electrical resistance of titania nanotubes with
hydrogen exposure, Adv. Mater. 15 (78) (2003) 624627.
[9] O.K. Varghese, G.K. Mor, C.A. Grimes, M. Paulose, N. Mukherjee, A titania
nanotube-array room-temperature sensor for selective detection of hydrogen
at low concentrations, J. Nanosci. Nanotech. 4 (7) (2004) 733737.
[10] O.K. Varghese, M. Paulose, K. Shankar, G.K. Mor, C.A. Grimes, Water-photolysis
properties of micron-length highly-ordered titania nanotube-arrays, J.
Nanosci. Nanotech. 5 (7) (2005) 11581165.
[11] M. Paulose, G.K. Mor, O.K. Varghese, K. Shankar, C.A. Grimes, Visible light
photoelectrochemical and water-photoelectrolysis properties of titania
nanotube arrays, J. Photochem. Photobiol. A: Chem. 178 (1) (2006) 815.
[12] I. Paramasivam, J.M. Macak, A. Ghicov, P. Schmuki, Enhanced photochromism
of Ag loaded self-organized TiO2 nanotube layers, Chem. Phys. Lett. 445 (46)
(2007) 233237.
[13] K. Shankar, K.C. Tep, G.K. Mor, C.A. Grimes, An electrochemical strategy to
incorporate nitrogen in nanostructured TiO2 thin lms: modication of
bandgap and photoelectrochemical properties, J. Phys. D: Appl. Phys. 39 (11)
(2006) 23612366.
[14] J.H. Park, S. Kim, A.J. Bard, Novel carbon-doped TiO2 nanotube arrays with high
aspect ratios for efcient solar water splitting, Nano Lett 6 (1) (2006) 2428.
[15] R. Hahn, A. Ghicov, J. Salonen, V.P. Lehto, P. Schmuki, Carbon doping of selforganized TiO2 nanotube layers by thermal acetylene treatment, Nanotechnology 18 (10) (2007) (No.105604).
[16] S.G. Chen, M. Paulose, C. Ruan, G.K. Mor, O.K. Varghese, D. Kouzoudis, C.A.
Grimes, Electrochemically synthesized CdS nanoparticle-modied TiO2
nanotube-array photoelectrodes: preparation, characterization, and application to photoelectrochemical cells, J. Photochem. Photobiol. A: Chem. 177
(23) (2006) 177184.
[17] W. Choi, A. Termin, M.R. Hoffmann, The role of metal ion dopants in quantumsized TiO2: correlation between photoreactivity and charge carrier recombination dynamics, J. Phys. Chem. 98 (51) (1994) 1366913679.
[19] J.A. NavUo, G. Colo?n, M.I. Litter, G.N. Bianco, Synthesis, characterization and
photocatalytic properties of iron-doped titania semiconductors prepared
from TiO2 and iron(III) acetylacetonate, J. Mol. Catal. A: Chem. 106 (3) (1996)
267276.
[20] K.T. Ranjit, B. Viswanathan, Synthesis, characterization and photocatalytic
properties of iron-doped TiO2 catalysts, J. Photochem. Photobiol. A: Chem.
108 (1) (1997) 7984.
[24]
[25]
[26]
[27]
[28]
[29]
[30]
[31]
[32]
[33]
[34]
[35]
[36]
[37]
[38]
[39]
A. Di Paola, E. GarcUa-Lo?pez,
G. Marcs, C. MartUn,
L. Palmisano, V. Rives,
A.M. Venecia, Surface characterization of metal ions loaded TiO2 photocatalysts: structureactivity relationship, Appl. Catal. B: Environ. 48 (3)
(2004) 223233.