Thin Solid Films 519 (2011) 5494–5502

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Thin Solid Films

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / t s f

A photoelectrochemical study of CdS modified TiO2 nanotube arrays as photoanodes

for cathodic protection of stainless steel
Jing Li, Chang-Jian Lin ⁎, Jun-Tao Li, Ze-Quan Lin
State Key Laboratory of Physical Chemistry of Solid Surfaces, and College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China

a r t i c l e i n f o a b s t r a c t

Article history: An electrodeposited CdS nanoparticles-modified highly-ordered TiO2 nanotube arrays (CdS–TNs) photoelec-
Received 22 May 2010 trode and its performance of photocathodic protection are reported. The self-organized TiO2 nanotube arrays
Received in revised form 27 March 2011 are fabricated by electrochemical anodization in an organic–inorganic mixed electrolyte and sensitized with
Accepted 29 March 2011
CdS nanoparticles by electrodeposition via a single-step direct current. The morphology, crystalline phase,
Available online 6 April 2011
and composition of the CdS–TNs films were characterized systematically by scanning electron microscopy, X-
Keywords:
ray diffraction, X-ray photoelectron spectroscopy, and ultraviolet–visible (UV–Vis) spectroscopy, respective-
Titanium oxide ly. The photoelectrochemical performances of the CdS–TNs film under illumination and dark conditions in
Nanotube arrays 0.5 M NaCl solution were evaluated through the electrochemical measurements. It is indicated that the TNs
Anodization incorporated by CdS effectively harvest solar light in the UV as well as the visible light (up to 480 nm) region.
Cadmium sulfate It is supposed that the high photoelectro-response activity of the CdS–TNs is attributed to the increased
Photoelectrochemical measurements efficiency of charge separation and transport of electrons. The electrode potentials of 304 stainless steel
Cathodic protection coupled with the CdS–TNs is found to be negatively shifted for about 246 mV and 215 mV under UV and white
Steel
light irradiation, respectively, which can be remained for 24 h even in darkness. It is implied that the CdS–TNs
are able to effectively function a photogenerated cathodic protection for metals both under the UV and visible
light illumination.
© 2011 Elsevier B.V. All rights reserved.

1. Introduction approach to enhance their photoresponse in the UV region as well as

TiO2 has been broadly investigated in water splitting [1], dye-
sensitized solar cells [2,3], photocatalysis [4], and sensors [5] on the
basis of its chemical stability and unique functional properties.
Nevertheless, the wide bandgap of TiO2 limits its photocatalytic
properties in the ultraviolet (UV) region. Various approaches were
developed to extend the light harvesting region of TiO2, including
doping with other impurities (such as N, C, and S) [6,7] and coupling
with low bandgap semiconductors [8,9]. Small bandgap semiconduc-
tors, such as CdS [10], CdSe [11], PbS [12], PbSe [13] and InP [14], have
been introduced into mesoporous TiO2 films as sensitizers of the
photoelectrodes. Presently, TiO2 nanotubes prepared by anodic
oxidization are gaining extraordinary interest and were considered
to be the promising photocatalyst [15–18]. Compared with any other
titania nanoparticles (NPs), the highly ordered TiO2 nanotube arrays
(TNs) are suggested to be superior in chemical and photoelectro-
chemical performance, due to their unique architectural characteri-
zation of one-dimensional channel for carrier transportation, in which
the recombination of e−–h+ is expected to be reduced. Coupling TNs
electrodes with the CdS semiconductor seems to be a promising
⁎ Corresponding author. Tel.: + 86 592 2189354; fax: + 86 592 2186657.
E-mail address: cjlin@xmu.edu.cn (C.-J. Lin).
visible light [19–28].
Recently, intensive efforts have been undertaken to develop TiO2
coatings on metals or composites of nano TiO2 with other dopants for
the photogenerated cathodic protection of metals under UV illumi-
nation [29–34]. Yuan and Tsujikawa first reported the cathodic
protection of sol–gel derived TiO2 coating on a copper substrate [29].
Many investigations were carried out on the other substrates, such as
stainless steel (SS) by using pure TiO2 [31], TiO2–WO3 [32], TiO2–SnO2
[33], TiO2–CeO2 [34], N–S–Cl-modified nano-TiO2 [35] composite
films, TiO2 nanotubes [36,37] and TiO2 nanowires [38,39] as
semiconductor photoanodes. The principle of photocathodic protec-
tion is that when a metal coated with a thin TiO2 coating is exposed to
UV irradiation, electron–hole pairs are generated in the TiO2 coating.
The photogenerated electrons transfer to the metal substrate thereby
making its electrode potential more negative than its corrosion
potential. Furthermore, in this case, titania does not get consumed
because the anodic reaction is not the decomposition of TiO2 itself but
the oxidation of water and/or adsorbed organic species by the
photogenerated holes, unlike a sacrificial-type cathode protection
[34,40]. However, some critical challenges remain in photogenerated
cathodic protection, including (1) low efficiency of photo-electric
conversion in natural sunlight, (2) high recombination of photo-
generated e−–h+ pairs, and (3) elimination of photogenerated
cathodic protection in dark condition. It is highly required to improve

0040-6090/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.tsf.2011.03.116
 J. Li et al. / Thin Solid Films 519 (2011) 5494–5502
the visible response of TiO2 films as photoanodes for application in
photocathodic protection, and to keep the cathodic protection even
under dark condition from the practical aspect.
To date very few reports are found on the modification of these
highly ordered TNs using CdS for photogenerated cathodic protection
[41]. In the present work, the TiO2 nanotube array photoanode was
fabricated by self-organized process under potentiostatic conditions
in a glycerol and deionized (DI) water solution containing a small
amount of NaF [42]. Then the TNs was modified by an electrochem-
ically synthesized CdS–NPs film after electrodeposited Cd2+ in
dimethyl sulfoxide (DMSO) containing sulfur in elemental form. The
photoelectrochemical properties of the TNs photoelectrodes before
and after CdS nanoparticle-modification were examined in detail. The
cathodic protection activity was investigated when a 304-type SS was
coupled with the CdS–TiO2 nanotube arrays (CdS–TNs/304 SS) under
the UV–Vis light illumination and dark condition, in 0.2 M Na2SO4 and
0.5 M NaCl solution. The results were discussed by comparing the
cathodic protection performance for the different modifications of
TNs.
2. Experimental details
2.1. Preparation of TNs films
Titanium sheets of 2 mm in thickness and purity of 99.5% were
used. Prior to anodization, the titanium sheets (10 mm × 15 mm)
were mechanically ground with No. 400–1500 emery papers
gradually, then degreased in an ultrasonic bath in acetone, anhydrous
ethanol and DI water successively, followed by rinsing with DI water
and drying in air. Anodic films of TiO2 nanotubes were grown from the
surface of the titanium sheet by potentiostatic anodization at 25 V for
2–5 h using a platinum sheet as a counter electrode. The electrolytes
were 0.5 wt.% NaF and 0.2 M Na2SO4 in a mixed solution containing
glycerol (1,2,3-propanetriol) and DI water. Unless otherwise stated,
the volumetric ratio of glycerol and DI water was 2:1 (v/v). The
anodization experiments were performed under stirring condition
and at room temperature. After anodization, the samples were rinsed
with DI water. The as-anodized TiO2 nanotubes were amorphous.
They were subsequently annealed at 450 °C in air ambient for 2 h with
heating and cooling rates of 5 °C/min to induce crystallization of
anatase.
2.2. Preparation of CdS–TNs Films
The CdS–TNs were prepared by plain direct current (DC) electro-
chemical deposition method using a two-electrode system compris-
ing a TNs films as working electrode (1 × 1 cm2) and a Pt foil as
counter electrode. A mixed solution of 0.01 M CdCl2 in dimethyl
sulfoxide (DMSO) with saturated elemental sulfur was used as the
electrolyte [28]. Prior to the electrodeposition, two processes were
performed to completely dissolve elemental sulfur. First, the mixed
solution was bubbled with flowing N2 for 30 min in order to remove
O2 and any moisture within the solution. Second, the solution was
persistently stirred for 2 h for an even mixing. The temperature was
maintained at 110 °C. Then CdS was cathodically electrodeposited at
the optimum constant DC density of 0.5 mA cm− 2 for 5–15 min.
Subsequently, the samples were immediately removed from the
electrolyte and sequentially rinsed with hot DMSO, acetone and
double-distilled water, and finally dried in air at room temperature.
2.3. Characterization of CdS–TNs electrode
The morphologies of the samples were observed by a field
emission scanning electron microscope (SEM, LEO-1530) and trans-
mission electron microscopy (TEM, Tecnai-F30). The crystalline
structure of the samples was identified by x-ray diffraction (XRD,
5495
Philips, Panalytical X'pert, Cu KR radiation). The elemental composi-
tion of the nanotube array films was analyzed by X-ray photoelectron
spectroscopy (XPS, VG, Physical Electrons Quantum 2000 Scanning
Esca Microprob, Al Kα radiation) combined with 4 keV Ar+ depth
profiling. Photoelectrochemical measurements were carried out in
0.2 M Na2SO4 using an LHX 150 Xe lamp, a SBP 300 grating
spectrometer, and an electrochemical cell with a quartz window.
The wavelength-dependent spectral response was measured in a
three-electrode configuration with a platinum wire counter-electrode
and a reference saturated calomel electrode (SCE) at zero bias (VS
SCE) in the range of 250–700 nm. The photoabsorption properties
were recorded with a diffuse reflectance UV–visible spectrometer
(DRS) (Varian, Cary 5000).
2.4. Photoelectrochemical characterization
The homemade photoelectrochemical measurements were con-
ducted using a Princeton Applied Research Model 263A potentiostat/
galvanostat with an M5210 lock-in amplifier/chopper setup (using a
chopper frequency of 34 Hz) connected to an SBP 300 grating
spectrometer with an LHX 150 W Xe lamp as the source of
illumination. The photocurrent spectra measurements were per-
formed in a three-electrode experimental system. The as-synthesized
photoanodes with an active area of 1 cm2 were used as the working
electrode, a SCE and a platinum wire served as the reference electrode
and counter electrode, respectively.
To investigate the performance of photogenerated cathodic protec-
tion of the as-prepared photoanodes, the photogenerated potential
changes of the 304 SS electrode coupled with photoanode in the
presence and absence of light illumination were measured. The
photoelectrochemical setup included two cells, which was similar to
the work previously reported by Z.Q. Lin et al. [41]. Briefly, one cell
was for the as-prepared CdS–TNs photoanode and the other was for
the 304 SS electrode, as shown in Fig. 1. A Cu wire was used to couple
the two electrodes, and the two cells were connected by a salt bridge
(1 M KCl in agar contained in a U-type glass tube) to complete the
circuit. A SCE and a platinum foil served as the reference electrode
and counter electrode, respectively. The electrolyte in the photoanode
cell was 0.2 M Na2SO4, while in the corrosion cell was 0.5 M NaCl. The
surface area of 304 SS electrode was 1 cm2 and the CdS–TNs was 1.5 cm2
exposure to air. The photopotential was obtained when the open circuit
potential (OCP) reached a stable value under an illumination.
The measurements of Mott-Schottky, polarization curves and
electrochemical impendence spectroscopy (EIS) were conducted
using an Autolab PGSTAT 30 electrochemical measurement system.
The setup used in measurement was the same as OCP tests. The
potential swept amplitude was ±120 mV at the OCP and the scan rate
of 0.167 mV/s for the polarization measurements. The EIS was
Fig. 1. Schematic illustration of the experimental setup for photoelectrochemical
measurements.
5496 J. Li et al. / Thin Solid Films 519 (2011) 5494–5502

Fig. 2. (a) and (b): Typical SEM images of the top and cross-sectional views of the TNs electrode; (c) and (d): CdS–TNs after CdS electrochemical deposition at 0.5 mA cm− 2 for
10 min. (e) and (f): TEM images of CdS–TNs; and (g): the corresponding EDX spectrum.
 J. Li et al. / Thin Solid Films 519 (2011) 5494–5502
measured in the frequency range between 105 and 10− 3 Hz with an
amplitude 10 mV at OCP using five points/decade. The impedance
data of the films were fitted and interpreted by the EIS fitting software
built-in Autolab Electrochemical System. All experiments for the
different specimens were done in triplicate to confirm the reproduc-
ibility of the measurements.
3. Results and discussion
3.1. Characterization of CdS–TNs films
The morphologies of the TiO2 nanotube films were examined by
SEM. Fig. 2(a) is a typical SEM image of the as-synthesized TiO2
nanotube film, which reveals a regularly arranged pore structure of
the film. These pores have a uniform size distribution around 125 nm.
Fig. 1(b) is a cross-sectional view of the film and shows that the film is
composed of well-aligned nanotubes of about 3.5 μm in length which
grow vertically from a Ti substrate. Fig. 2(c) is SEM images of the
prepared CdS–TNs after CdS electrodeposition at 0.5 mA cm− 2 for
10 min. It is clearly indicated that TNs are extensively covered with a
relatively uniform layer of CdS NPs with diameters of about 100 nm
and many CdS NPs (marked with arrows) have incorporated into the
TNs. While the wall thickness of the CdS/TNs was similar to that of the
TNs. From the side-view image (Fig. 2(d)), the high-dispersive coating
of CdS NPs can be observed.
The detailed microscopic structure of the CdS–TNs was further
investigated by TEM. Fig. 2(e) and (f) shows the TEM images of CdS
NPs inside TNs and isolated CdS NPs deposited on top of TNs. It clearly
indicates that the tubes are transparent in nature (marked with white
arrows) and the CdS NPs (dark spots, marked with black arrows) have
been deposited into the channels of the TNs. This will support our
earlier observation in the SEM images, The composition of the NPs is
determined by an energy dispersive x-ray spectroscopy (EDX)
experiment, which is carried out in the TEM. The EDX spectrum of
the CdS (10 min)/TNs was shown in Fig. 2(g), the characteristic peaks
are associated with Ti, O, S and Cd, where Ti and O peaks are from TNs,
Cd and S peaks result from CdS NPs. While peaks associated with C
and Cu are from the copper grid and supporting C film used in TEM
experiments. The quantitative analysis reveals the atomic ratio of Cd
and S is close to unity, indicating the deposited materials are CdS.
3.2. Chemical composition analysis
The crystal structure of CdS–TNs was examined by XRD experi-
ments. Fig. 3 shows a comparison of XRD patterns of annealed TNs
Fig. 3. XRD patterns of the annealed TNs at 450 °C (a), and CdS–TNs after CdS electro-
chemical deposition for 10 min (b) and 15 min (c), respectively. (A—anatase, C—CdS,
and T—titanium.)
5497
with or without CdS crystal deposition. It is apparent that the all
annealed TNs samples exhibit the crystalline phase of anatase TiO2.
The characteristic peaks (curves b and c) appeared at the diffraction
angle of 26.6°, 28.2° and 43.9° can be assigned to the pure CdS
hexagonal structure with crystal faces of (002), (101) and (110) [27].
These characteristic peaks increase their intensity for longer deposi-
tion times, which indicates that the number of CdS nanospheres also
grows up. These XRD results confirmed the SEM observation. The
other diffraction peaks of CdS are not clearly resolved because of
overlapping with that of anatase TiO2.
In order to further indicate the chemical compostion and oxidation
state of CdS on the decorated TNs, the XPS measurements were
performed. The survey spectrum and Cd 3 d and S 2p core level are
presented in Fig. 4, respectively. The general scan spectrum of XPS
(Fig. 4(a)) of the CdS–TNs shows sharp XPS peaks for Ti, O, Cd, S and
also C. Fig. 4(b) and (c) is Cd 3 d and S 2p core level XPS spectra,
respectively. The Cd 3 d5/2 and Cd 3 d3/2 peaks centered at 405.2 and
411.9 eV with a spin–orbit separation of 6.7 eV, is in good agreement
with the previously published values for CdS [43]. The S 2p core level
spectrum indicates that there are two chemically distinct species in
the spectrum. The peak at 161.9 eV is corresponding to S2− of CdS NPs,
the peak at 168.4 eV is assigned to the presence of S6+ replacing Ti4+
in the TiO2 lattice, which is well inline with the previously published
values of the S 2p signal for CdS in Refs. [19,44]. The atomic
concentrations for S and Cd in surface layer are 10.11% and 26.37%.
The atomic concentrations for S and Cd in inner layer of 200 nm depth
are 8.94% and 15.25%, respectively. The results prove that the
deposited CdS amount is inhomogeneous and decreases with
increasing depth of the TNs. These results can further confirm that
the obtained samples are composed of CdS and TiO2.
3.3. Photoelectrochemical characterization
Fig. 5 presents the comparison of the photocurrent spectra of the
pure TNs electrode and the CdS–TNs electrodes prepared under
different elelctrodeposition times. It is apparent that the pure TNs
samples have a photo-response wavelength lower than 400 nm due to
its band-gap of 3.2 eV (curves a and b). The decoration of CdS NPs
with a smaller energy band-gap (2.4 eV) can significantly extend the
photo-response range from 280 nm to 500 nm. Moreover, the CdS–
TNs electrodes can also greatly increase the photocurrent response
under UV light, especially for the samples obtained under 10 min
electrodeposition (curve d). For example, the photocurrents of the
CdS–TNs electrodes with 5 min and 10 min CdS electrodeposition
were 4300 and 6200 nA, respectively, which were much larger than
that of pure TNs (curve b). In addition, the intensity of photocurrent
increases with the increase of the electrodeposition time.
Firstly, according to the previous report [45], the overall photo-
conversion efficiency of a multiband gap semiconductor depends on
the position of its conduction and valence bands as well as their
geometrical arrangement. Because the conduction band of TiO2 is
more anodic than that of the CdS. This thermodynamic conditions
favor the efficient electron transfer between the CdS and TiO2. When
the system is under UV–vis irradiation, both semiconductors are
excited. The photon-generated electrons are injected from conduction
band (CB) of CdS to CB of TiO2, at the same time, the holes transfer
from valence band (VB) of TiO2 to VB of CdS, respectively.
Additionally, more photoelectrons are generated from TNs by
harvesting UV photons. In this case, a high concentration of electrons
is obtained in the conduction band of TiO2 compared to TiO2 alone.
Moreover, the highly ordered nanotubular architecture of the
composite contributes to prolong the lifetime of charge carriers. As
a result, the photoexcited electrons and holes can be effectively
collected by TiO2 and CdS, i.e. the heterojunction CdS–TNs facilitates
separation of the photogenerated electrons and holes. The holes (from
both CdS and TiO2) transferred to the solid–liquid interface to
5498 J. Li et al. / Thin Solid Films 519 (2011) 5494–5502

Fig. 5. A comparison of photocurrent spectra of the pure TNs and various CdS–TNs
electrodes.

able to make the TNs to be more sensitive to the UV and visible

spectrum, and the CdS–TNs films are capable to harvest solar light
much more effectively than the pure TNs.

3.4. Characterization of CdS–TNs films by Mott-Schottky measurements

In order to prove that the band bending really taken place in the
CdS–TNs composite framework, the Mott-Schottky measurements
were performed at the optimum frequency of 1000 Hz [47], shown in
Fig. 6. Donor densities and flatband potentials were determined by

Fig. 4. XPS spectrum of the CdS–TNs films. (a) Total spectrum, (b) Cd 3d XPS core level
spectrum, and (c) S 2p XPS core level spectrum.

generate protons from the solution. In these processes, the photo-

current increased remarkably in the UV region.
Secondly, the uniform dispersion of CdS NPs with suitable size
decorated onto the TiO2 nanotubes allows for a higher electron
transfer and lower electron–hole recombination which leads to
Fig. 6. Comparison of Mott-Schottky plot obtained at 1 KHz frequency for the TNs and
enhance light harvesting at the directly grown CdS–TNs heterojunc- CdS–TNs film electrodes in 0.2 M Na2SO4. (a) Plotting (C) vs E; and (b) Plotting (1/C2)
tions [46]. The results suggest that the electrodeposited CdS NPs is vs E.
 J. Li et al. / Thin Solid Films 519 (2011) 5494–5502 5499

measuring the capacitance of the CdS–TNs-electrolyte junction as a 3.5. UV–vis absorption spectroscopy
function of voltage (referred to a SCE reference electrode,) using the
following equation: A comparison of the optical absorption spectra for the CdS–TNs
films with that of the plain TNs is shown in Fig. 7. It can be seen
 
1 2 κT that the pure TNs exhibit a fundamental absorption edge at about
= E−EFB − ð1Þ 380 nm, corresponding to the band-gap energy of 3.2 eV. Compara-
C 2 εCdS–TNs ε0 e0 ND e0
tively, the CdS–TNs samples exhibit an enhanced absorbance both in
UV and visible regions, indicating the effective photoabsorption
(with ε0 being the permittivity of free space (8.85 × 10− 12 F m− 1), εTNs
property for such ordered composite structure which combines the
(48 for anatase of TiO2) and εCdS–TNs (5.7) the relative permittivity
absorption properties of TNs in the UV region and CdS NPs in the
of the semiconductor electrode [48,49], e0 the elementary charge
visible region.
(1.602 × 10− 19 C), ND the donor density, E the applied potential, EFB
By increasing the deposition time (i.e., increasing the size of the
the flatband potential, k is Boltzmann's constant (1.38 × 10− 23 J K− 1),
CdS NPs), the λ max shifted to the visible light region (red shift),
T the temperature of operation, and C the space charge capacitance).
which is due to the quantum size effect [45]. For example, from Fig. 7
In accordance with Eq. (1), we have
(curves b and c), one can see that the absorption edge of CdS–TNs
  electrodes is red-shifted into the visible region, the absorption peaks
2 2 κT
ND = C E−EFB − ð2Þ extended to 500 nm, combined with a calculated edge bandgap of
εCdS–TNs ε0 e0 e0 about 2.4 eV, it is a typical bandgap value for bulk CdS state. This is
well in line with the results of visible region extension shown in
when photocurrent spectra. As regards the sample which was electrode-
posited CdS for 10 min (curve d), its absorption peaks are further red-
1 shifted, with the absorption peak extending to 550 nm. This finding is
K= ð3Þ
C 2 ðE−EFB −κT=e0 Þ in line with DRS results of CdS modified TiO2 nanotube in previous
reports [19]. The spectrum of red-shift can be attributed to the
aggregation of annealing CdS NPs and the formation of valence-band
we have
tail states.
It can be concluded that the formation of CdS NPs into the TNs
2
ND = : ð4Þ leads to a new visible absorption extending beyond the TiO2 band
εCdS–TNs ε0 e0 K
gap absorption around 500 nm wavelength. This suggests that the
CdS–TNs heterojunction structure thus alters its electronic and optical
A Mott-Schottky plot of C vs. potential (E) is shown in Fig. 6(a). It is properties [53]. The enhanced ability to absorb visible-light of the
clear that the capacitance of CdS–TNs sample is larger than that of ordered CdS–TNs films makes it a promising photoanodes for photo-
undecorated TNs, suggesting that there are more charge carriers, cathodic protection applications.
which is conducive to the injection of holes from the CdS–TNs
heterojunction to electrolyte. 3.6. Polarization measurements
Moreover, the capacitance is decreased with the increase of
potential. According to the explanation of depletion layer in reference Fig. 8 shows the comparison of polarization curves for the bare
[50,51], this indicates that the majority carriers transfer from CdS–TNs 304 SS in darkness (curve a), 304 SS coupled to pure TNs (curve b),
composite semiconductor to the electrolyte, this process leads to the CdS–TNs film after CdS electrochemical deposition for 5 min (curve d)
decrease of capacitance, as a result, a depletion zone present in the and 10 min (curve c), in the presence of white light illumination,
space charge layer, at this stage, the number of majority carriers is respectively. It is clear that the polarization potential exhibits a
reduced with the increasing of potential, and the space charge layer is remarkable negative shift when the 304SS electrode is connected with
featured by the insulator character at the later stage of the variation of an illuminated photoanode. It is noted furthermore that the corrosion
potentials. potentials of 304 SS coupled with CdS–TNs are much negative than
The plotting of 1/C2 vs. E is shown in Fig. 6(b), the gradient of that of undecorated TNs, the finding is well in line with the results of
the linear can be used to calculate the donor density (ND). The K for our previous work [38].
the pure TNs(KTNs) and CdS–TNs(KCdS–TNs) is KTNs = 1.43 × 1010 and
KCdS–TNs = 1.05 × 108, respectively. We have NDTNS = 2.06 × 1018 and
NDCdS–TNS = 2.24 × 1022. It is obvious that NDCdS–TNs is 4 order of
magnitude larger than that of NDTNs depends on the Eq. (4), this can be
explained as follows:
Because the conduction band edge of CdS is above that of the
TiO2 nanotube, when CdS is combined with TiO2, local band
bending occurs at the CdS/TiO2 interface and a local electric field is
established [52]. When illuminated, the CdS NPs effectively
absorb visible light and generate electrons and holes pairs. The local
electric field at the CdS–TiO2 interface pushes the photogenerated
electrons and holes into the CB of TiO2 and the VB of CdS, respectively.
And the photoexcited electrons and holes can be effectively collected
by TiO2 and CdS, that is to say, the heterojunction CdS–TNs can
facilitate the separation of photogenerated electrons and holes, the
photoactivity of the TNs will be improved. In addition, because the
TNs are crystalline and well-aligned on the Ti substrate, the injected
electrons transfer effectively to the collector electrode (Ti substrate).
Therefore, the donor density of CdS–TNs is larger than that of Fig. 7. The UV–vis absorption spectra of TNs and CdS–TNs samples after electro-
undecorated TNs. deposited for different time.
5500 J. Li et al. / Thin Solid Films 519 (2011) 5494–5502

Fig. 8. Comparison of the polarization curves for CdS–TNs/304 SS and pure TNs/304 SS in
the presence and absence of white light illumination and for bare 304 SS in the dark.
(a) Bare 304 SS in the dark. (b) Pure TiO2/304 SS in the presence of illumination (c and d).
CdS–TNs/304 SS in the presence of white light illumination, the CdS deposition times
are 5 min (d) and 10 min (c), respectively.

According to the fundamental definition of Voc in reference [54],

this value is limited by the difference of the conduction band edge of
TiO2 and the redox potential of the electrolyte and increases with the
amount of electrons in the conduction band of TiO2 (the position of
the Fermi level). Because the crystalline nature and the film geometry
of the TNs allow a fast and efficient transfer of the photogenerated
electrons from CdS NPs to the Ti substrate, leading to a less electron–
hole recombination and a higher photocurrent efficiency. Moreover,
the suitable band position of CdS and TiO2 can efficiently separate
electron–hole pairs [28], the energy barriers formed in the composite
CdS–TNs may be favorable for the path of enough electrons to move to
the 304 SS electrode. In the present case, as a result, the potential is
dependent on the amount of charge carriers at the conduction band of
Fig. 9. Nyquist plots of electrodes samples in 0.5 M NaCl solution (a) in comparison
TiO2, which increases with the amount of CdS incorporated into the for the TNs/304SS, CdS–TNs/304 SS and bare 304 SS in darkness, respectively.
structure. (b) Comparison for pure TNs/304 SS and CdS–TNs/304 SS under UV and white light
Additionally, as can be seen in Fig. 8, the polarization cathodic and irradiations. The insets of (a) and (b) are the corresponding equivalent circuits.
anodic current densities show notable increase when coupled to
photoanode either with or without light illumination, compared with
markedly compared with that of bare 304 SS electrode (Fig. 9(a)). This
that of bare 304 SS electrode. The increase of current density is also
is attributed to the injection of photogenerated electrons to the 304 SS
attributed to the enhancement of electrochemical reaction at the
electrode, resulting in a promotion of electrochemical reaction, and
interface resulted from the polarization of photogenerated electron [31].
showing the values of resistance (Rt) decreases 2–3 orders of
magnitude and the values of Q increased nearly two orders.
3.7. Impedance measurements
According to the mechanism of cathodic protection of metals,
under illumination, the photogenerated electrons in CB of TiO2 films
EIS as a powerful non-destructive test is capable of obtaining
transfer to the 304 SS, which results in a potential shift of metal
significant quantitative and qualitative data of corrosion [55]. Fig. 9(a)
substrate to the corrosion immunity region. And the rate of the
displays Nyquist plots of two different TiO2 films coupled 304 SS and
electrochemical dissolution reaction at the surface of metals is
bare 304 SS under dark condition. The arc shape is almost
suppressed and the resistance of the TNs film is decreased. On the
unchangeable compared to that of bare 304 SS. Considering the
other hand, the photogenerated holes migrate to the interface of SS/
plots with only one impedance arc, the relevant spectra could be
electrolyte, reacting with the H2O molecules as a hole scavenger
modeled by the equivalent circuit shown in the inset of Fig. 9a. Where
forming O2 and H+ in neutral NaCl solution [35], which cause Q dl and
Rs represents solution resistance, Rt charge transfer resistance and Q dl
Rt to be changed. The results revealed that the excess electrons on the
double layer capacitance. The simulate values are given in Table 1. The
Fermi level of metals on illumination may provide an effect of cathodic
Rt for the CdS–TNs coupled 304 SS, TNs-coupled 304 SS, and bare 304
protection for the metals.
SS is 4.42 × 103, 1.12 × 103, and 1.54 × 104 Ω, respectively. The Nyquist
plots illustrate that the CdS–TNs electrode also have a better corrosion
Table 1
protection for 304 SS according to the RC arcs with a larger value of
Fitting impedance parameters of Nyquist plots using the equivalent circuit in Fig. 9(a).
the resistance.
Fig. 9(b) shows the Nyquist plots of different samples coupled to Electrodes Rs (Ω cm2) Rt (Ω cm2) Q (Ω− 1 S−n cm− 2) n
304 SS under irradiation, and the equivalent circuit of the system is CdS–TNs/304 SS a
8.08 4.42 × 103
2.24 × 10− 5 0.85
given in the inset of the same figure. The fitting values are TNs/304 SS a 7.48 1.12 × 103 7.92 × 10− 5 0.99
summarized in Table 2. It is found that, the diameter of impedance Bare 304 SS a 13.60 1.54 × 104 2.33 × 10− 5 0.84

arcs of 304 SS coupled with CdS–TNs or pure TNs electrodes decrease a

In dark condition.
 J. Li et al. / Thin Solid Films 519 (2011) 5494–5502
Table 2
Fitting impedance parameters of Nyquist plots using the equivalent circuit in Fig. 9(b).
Electrodes Rs (Ω) Qc Rc (Ω) Q dl
Y0 n Y0
CdS–TNsa 13.84 8.32 × 10− 5 0.78 4.97 × 104 5.65 × 10− 5
CdS–TNsb 13.69 4.06 × 10− 5 0.82 9.90 × 104 9.70 × 10− 3
TNsa 14.63 3.98 × 10− 4 0.65 4.80 × 104 1.33 × 10− 5
TNsb 13.58 2.84 × 10− 4 0.64 1.40 × 105 1.92 × 10− 5
a
Under white light illumination.
b
Under UV light illumination.
From the comparison of the Nyquist plots of 304 SS coupled with
CdS–TNs electrode under UV and visible light illumination, it is found
that the arc shape is similar but the diameter of the arc for CdS–TNs
under white light (Fig. 9(b), curve a) markedly decreases compared
with under UV illumination (Fig. 9(b), curve b), on the contrary, the
diameter of arc for pure TNs is much smaller under UV light
irradiation (Fig. 9(b), curve d) than that of TNs under white light
(Fig. 9(b), curve c), indicating that the CdS–TNs samples yielded much
lower charge transfer resistance values when supplying a white light
illumination on the photoanode, suggesting that CdS NPs can sensitize
TNs films to make them more responsive to the visible spectrum of the
sunlight. It conversely agrees with the preceding discussion that the
pure TNs are more sensitive to the UV light, this is well in agreement
with the results of photocurrent spectrum. It is also indicated that the
CdS–TNs electrodes are able to provide more effective photocathodic
protection for 304 SS under visible light irradiation.
Because the unique nanotube structures can facilitate the propaga-
tion and kinetic separation of photogenerated charges carriers [22],
there are much more photogenerated electrons that transfer from
CdS–TiO2 electrode to 304 SS under white light illumination, thus
leading to a greater resistance decrease than that under UV light.
It is important to note that the heterostructure formed in the
interface of CdS and TNs is efficient for separation of photogenerated
electron–hole pairs and accelerates the photogenerated electron
transfer from the CB of CdS with narrow band-gap (2.4 eV) to the
CB of TNs with broad band-gap (TiO2 anatase, 3.2 eV) [27].
Furthermore, CdS–TNs are featured by a strong visible light
absorption at wavelength of visible light region (~540 nm). Based
on the above discussion, the experimental results of EIS do indicate
that CdS–TNs composite as photoanode coupled to 304 SS electrode
exhibits an anticorrosion effect in the presence of illumination. It is
surprised to know that, under the coupling with such photoanode, the
304 SS electrode can also be protected from corrosion when the light
is turned off. This is very useful from the practical aspect in the
protection of 304 SS electrode under the real outdoor conditions.
3.8. Performance of photogenerated cathodic protection
Fig. 10 depicts a comparison of the response of the photogenerated
potentials of 304 SS coupled to the TNs and CdS–TNs film electrodes,
respectively, under UV (λ = 360 nm) and white light illumination and
in the dark condition. It shows that the CdS–TNs electrodes are
capable of exhibiting a stronger photoeffect on the illumination with
UV and white light. As can be seen in Fig. 10 (curve b), when
illuminated by a UV light, the photogenerated potential of 304 SS
coupled to CdS (10 min)–TNs drops immediately to a much more
negative value of −207 mV than the initial dark potential of 304 SS
(+40 mV), as a result of the sudden creation of photogenerated
electron–hole pairs in the nano tubular CdS–TNs electrodes. After 1 h
of irradiation, then the light source was cut off, the photo-potential
switches back to a stable photopotential of −3.7 mV (vs SCE) in 2 h.
Then the irradiation was turned on, the electrode potential of 304 SS
immediately negatively shifts, it indicates again that the CdS–TNs
electrodes possess excellent photoeffect under the UV light illumina-
5501
Rt (Ω)
n
0.99 2.08 × 102
0.88 5.49 × 102
0.94 8.16 × 102
0.97 7.65 × 102
Fig. 10. Time dependence of photogenerated potential for 304 SS coupled with CdS–TNs
electrodes under white light (curve a) and UV illumination(curve b), TNs under UV
light (λ = 360 nm) (curve c), and in dark conditions.
tion. It is noted that these negative values of the photogenerated
potential can last for 24 h when illumination is turned off, implying
the possibility to remain a sufficient cathodic protection for the 304 SS
even in the dark condition for quite a long time. This can be attributed
to the superior storage capacity of the CdS–TiO2 composite tubular
architecture for the photogenerated electron–hole pairs.
In the case of non-deposited TNs (Fig. 10, curve c), the
photogenerated potential of 304SS coupled to the TNs film immedi-
ately negatively shifts under UV light irradiation and switches back
promptly to less positive values than its rest potential due to fast
charge recombination after the light is cut off. The shift of the
potential change of 304 SS was much less than that of 304 SS coupled
with the CdS–TNs nanofilms. The TNs has been recognized as one of
the predominant materials used for the photogenerated cathodic
protection of metals under irradiation [37]. Herein, not only could the
CdS–TNs films effectively provide cathodic protection for 304 SS in
NaCl solution under UV illumination, but also its performance in some
cases was even more superior to that of TNs observed in the dark.
While under visible light (Fig. 10, curve a), the electrode potential
decreased immediately and stabilized at the photopotential of
−85 mV compared to the initial potential (i.e. OCP) of TiO2 coupled
304 SS in the dark (~40 mV), resulted from the transfer of the photo-
generated electron–hole pairs excited from the CdS–TNs photoanode
onto the surface of 304 SS. When the visible light was removed, the
electrode potential recovered only slightly. Interestingly, the negative
electrode potential shift was maintained for a long period in the dark,
that is, the photogenerated cathodic protection could last for a
reasonable time even without any illumination.
Comparing curve (a) with curve (b), it can be seen that, when the
sample of 304 SS coupled with CdS–TNs electrode was irradiated by
UV, the electrode potential shifted to a more negative value. However,
the rest potentials of the sample switched promptly back to less
negative values than that of the sample under the white light
illumination because of fast charge recombination and stoppage of
charge transfer after the light was removed. Notably, the electrode
potential recovery of the sample was much more evident after UV
irradiation (Fig. 10, curve b) than that of the sample after visible light
irradiation (Fig. 10, curve a), indicating that the CdS–TNs films had
more superior charge storage property under visible light irradiation
(λ N 400 nm) than under UV illumination.
The excellent photoresponse performance for the CdS sensitized
TNs composites is attributed to its low band gap energy, fast electron
transfer velocity, large surface area and ordered mesoporous
structures [53]. A large surface area will effectively promote the
separation efficiency of the electron–hole pairs and enhance the light
5502 J. Li et al. / Thin Solid Films 519 (2011) 5494–5502
harvesting. Meanwhile, an optimal tubular structure can give rise to
more available surface active sites, and consequently lead to a higher
interfacial charge carrier transfer rate and collect for maximizing the
quantum yield [56]. The possible reasons for the enhancement of the
strong absorption within the solar spectrum of CdS–TNs hetero-
structure film are due to the coupling effects of CdS NPs and TNs films.
Because the conduction band level of CdS is slightly higher than that of
TiO2 and the CdS NPs are evenly-dispersed on the oxide surface with
strong covalent bonding which can improve the efficiency of electron
transfer from sensitized CdS NPs to a host TNs matrix [57]. The band
position of CdS and TiO2 is a type-II band alignment that is expected to
efficiently separate electron–hole pairs [58]. When exposed to solar
irradiation with longer wavelength (N410 nm), photoexcited elec-
trons were generated in the small band gap CdS NPs (2.4 eV) and then
transferred to the TNs sequentially, resulting in a higher utilization of
solar energy. Under white light irradiation, electrons excited from the
VB of CdS to the CB of CdS and then transferred to the CB of TiO2
nanotube sequentially, while the VB holes in TiO2 nanotubes injected
to the VB of CdS [44], which results in an efficient electron–hole
separation. The above discussion is helpful to further understand why
the CdS–TNs layers exhibit a strong photoresponse to visible light
irradiation and maintain an effective photogenerated cathodic
protection for a long period of several hours even without illumina-
tion. A further investigation of the stability and application of
photocathodic protection of CdS–TNs exposed to UV–visible light is
under performed and published in elsewhere.
4. Conclusions
In conclusion, we have prepared a free-standing CdS–TNs in DMSO
using a simple and feasible electrodeposition method. Compared
with the plain TNs, the CdS–TNs display an enhanced photocurrent
response even extended to 480 nm. The high photo-activity of this kind
of CdS–TNs composite semiconductor system was attributed to the
strong absorption within the solar spectrum and the effective decrease
in electron–hole pair recombination in a regular nanotube structure.
It is found that the electrode potentials of 304 SS coupled with the
CdS–TNs electrode in NaCl solution is significantly negative-shifted
under UV illumination and white light irradiation, the potential
negatively shift can be maintained for several hours even when the
illumination is cut off. It is indicated that the annealed CdS modified
TiO2 nanotube films are able to be developed as one of the most
promising alternative for cathodic protection of metals under
irradiation and dark conditions.
Acknowledgments
This work was supported by the National Natural Science
Foundation of China (51072170, 50731004, and 21021002), and
National High Technology Research and Development Program of
China (2009AA03Z327).
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