Applied Surface Science 258 (2012) 50385045

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Applied Surface Science

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Photoelectrochemical properties and photocatalytic activity of nitrogen-doped

nanoporous WO3 photoelectrodes under visible light
Yuyang Liu a , Ya Li b , Wenzhang Li a, , Song Han a , Canjun Liu a
a
Key Laboratory of Resources Chemistry of Nonferrous Metals (Ministry of Education), School of Chemistry and Chemical Engineering, Central South University, Changsha 410083,
China
b
College of Chemistry, Xiangtan University, Xiangtan 411105, China

a r t i c l e

i n f o

Article history:
Received 24 November 2011
Accepted 13 January 2012
Available online 21 January 2012
Keywords:
Tungsten oxide
Nanoporous photoelectrode
Nitrogen-doped
Photocatalytic activity

a b s t r a c t
In the present work, nitrogen-doped tungsten oxide (WO3 ) nanoporous photoelectrode was studied by
photoelectrochemical and photocatalytic methods in order to evaluate the photoactivity and the possibility of its application in solar photocatalysis. WO3 nanoporous photoelectrodes were prepared by
anodization of tungsten foil in NH4 F/(NH4 )2 SO4 electrolytes, followed by annealing in NH3 /N2 to incorporate N as a dopant. The crystal structure, composition and morphology of pure and nitrogen doped WO3
were compared using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron
microscopy (SEM). The results indicate that nitrogen can be doped successfully into WO3 nanoporous
photoelectrodes by controlling annealing temperature. Incident photon to current efciency measurements carried out on PEC cell with N-doped WO3 nanoporous photoelectrodes as anodes demonstrate a
signicant increase of photoresponse in the visible region compared to undoped WO3 nanoporous photoelectrodes prepared at similar conditions. In particular, the photocatalytic and photoelectrocatalytic
activity under visible light irradiation for newly synthesized N-doped WO3 nanoporous photoelectrodes
were investigated by degradation of methyl orange. The photoelectrocatalytic activity of N-doped WO3
nanoporous photoelectrodes was 1.8-fold enhancement compared with pure WO3 nanoporous photoelectrodes.
2012 Elsevier B.V. All rights reserved.

1. Introduction
As a promising material, tungsten oxide (WO3 ) has received
a great deal of attention due to its no-photo-corrosion, stability
in acid, and potential to absorb a reasonable fraction of the solar
spectrum [14]. In the past two decades, WO3 has been extensively studied for their fundamental science and a wide variety
of application in photovoltaics [57], photocatalysis [810], and
water splitting [1114]. However, due to the relatively large band
gap (2.63.0 eV), WO3 mainly absorbs in the near ultraviolet and
blue region of the solar spectrum. To overcome this limitation and
to enlarge its absorption range, many methods have been investigated, including noble metal deposition [1519], transition metal
doping [20,21], and dye sensitization [7,22]. It has been found
that WO3 doped with some elements, such as carbon, sulfur and
nitrogen would enhance photoresponse under visible irradiation
[2325]. Comparing the effect of above anion dopants through density of states calculations, nitrogen (N) doping has been identied

Corresponding author. Tel.: +86 731 8887 7364; fax: +86 731 8887 9616.
E-mail address: liwenzhang@csu.edu.cn (W. Li).
0169-4332/$ see front matter 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.apsusc.2012.01.080

as the most promising species because its p states mix with O 2p

states [26], resulting in a reduction of the band gap.
To the best of our knowledge, there are two synthetic routes
about the modication of WO3 by nitrogen, including sputtering
methods [24,27,28] or calcinations in the presence of ammonia
[23,29]. Paluselli et al. [27] reported that N-doped WO3 with a
band gap of 2.2 eV can be prepared by RF reactive sputtering, and
Cole et al. [28] reported N doping narrowed WO3 band gap from
2.5 eV to 1.9 eV in the same technique. In those synthesis routes,
N2 was used as the nitrogen sources for the preparation of Ndoped WO3 . The doping of nitrogen has reduced the energy band
gap efciently. However, the photoelectrochemical performance
of N-doped WO3 lms prepared by RF reactive sputtering is no
promising. Recent studies by Schmuki and co-workers [23] showed
that the photocurrent of N-doped WO3 lms by NH3 treatment is
signicantly enhanced in the visible light region. In their studies,
the N-doped WO3 lms were synthesized by a two step annealing
method, including annealed at 450 C for 1 h in ambient air step and
treated at 300 C in NH3 for 4 h step in sequence.
It is feasible that doping impurities into WO3 powder can
improve photocatalytic activity under visible light [20,21,30]. However, the separation problems of WO3 powder hold back its
utilization in the application. Therefore, many kinds of WO3 lms

Y. Liu et al. / Applied Surface Science 258 (2012) 50385045

on various substrates were used to substitute WO3 nanopowders as photocatalyst [8,31,32]. Fortunately, the recently reported
possibility to fabricate WO3 nanoporous lms provides a unique
opportunity for the photocatalysis application [1,4,3336]. In order
to obtain such nanostructure oxide layers, a new approach was
developed that is based on anodization of W in diluted F containing electrolytes. In our previous report [37], we investigated
the visible light photoelectrochemical properties of the ordered
nanoporous WO3 layers prepared in neutral NaF/Na2 SO4 strong
electrolytes by voltage stepping anodization. These nanostructured oxide layers have shown excellent corrosion resistance and
higher photocurrent conversion efciency as compared with compact anodic WO3 layers grown under comparable electrochemical
conditions.
In the present work, we describe the effect of nitrogen doping of
self-organized anodic nanoporous WO3 photoelectrodes obtained
by one step annealing in a NH3 /N2 gas mixture. The structural,
morphologic and photoelectrochemical properties of an efcient
N-doped WO3 as well as undoped WO3 photoelectrodes were evaluated. The photoelectrocatalytic activity of N-doped nanoporous
WO3 photoelectrodes was also evaluated by degradation of methyl
orange under visible light irradiation. To the best of our knowledge, this is the rst report on the visible photocatalytic activity of
N-doped nanoporous WO3 photoelectrodes. This work may offer
new insights on the photoactivity enhancement.

5039

of the samples were identied by X-ray photoelectron spectroscopy

(XPS, XSAM800, Kratos, Britain).
2.4. Photoelectrochemical measurement
In order to investigate the photoresponse of the N-doped WO3
nanoporous photoelectrodes, a standard three-electrode electrochemical cell with a at quartz window to allow illumination
was used for the photoelectrochemical and electrochemical measurements, which were performed in 0.5 M H2 SO4 (pH 0) by an
electrochemical workstation (Zennium, Zahner, Germany). A Pt
counter electrode and an Ag|AgCl|satd. KCl reference electrode
along with the working electrode completed the cell setup. The
potentials were swept linearly at a scan rate of 10 mV/s, and all
potentials in the photocurrent data below were quoted with respect
to this reference electrode. A 500 W Xe lamp (CHF-XM35, Trusttech
Co. Ltd., Beijing) served as the visible light source with an intensity
of 100 mW/cm2 . A 400 nm cutoff lter was placed into the path
of the Xe lamp to remove the UV irradiation. Photo-action spectra were recorded by using an apparatus comprising a Xe lamp
source (150 W, Oriel), a monochromator with bandwidth of 10 nm.
A focusing lens was equipped with monochromator to enhance the
incident light power on the photoelectrode. For the IPCE calculation, the absolute intensity of the incident light was measured by
a model BS2281 Si detector and the photocurrent was measured at
1.2 V vs Ag/AgCl (pH 0).

2. Experimental
2.5. Evaluation of photocatalytic activity
2.1. Preparation of WO3 nanoporous photoelectrodes
To produce anodic WO3 nanoporous photoelectrodes, we used
tungsten foils (99.95% purity, Alfa Aesar) with thicknesses of
0.05 mm as substrates. The tungsten foils were cleaned in four
15 min steps in acetone, isopropanol, methanol and nally deionized (DI) water and then dried in a nitrogen stream. The anodization
experiments were carried out in a two-electrode cell consisting of
a tungsten working electrode and a Pt counter electrode at room
temperature (25 1 C). The tungsten samples were anodized at
50 V in 1 M (NH4 )2 SO4 + 0.5 wt% NH4 F for 30 min. The cell voltage
was applied by a single step from the open-circuit potential to a
given value and was supplied by a direct current voltage source
(DH1719A-5, Dahua, China). The current between the working and
counter electrodes was measured by a digital multimeter (34401A,
Agilent) interfaced to a personal computer. After the electrochemical treatment, the samples were immediately rinsed with DI water
and then dried in a N2 stream. All solutions were prepared from
reagent-grade chemicals and DI water.

For the photocatalytic (PC) and photoelectrocatalytic (PEC)

degradation experiments, methyl orange (MO) was chosen as a target compound with an initial concentration of 20 mg/L. A 500 W
xenon lamp with a cutoff lter ( 400 nm) was employed as
the visible light source. The distance between the photoreaction
and lamp was 10 cm and the visible light intensity was about
100 mW/cm2 . The photoreacted solution was analyzed by recording variations of the absorption band maximum (508 nm) in the
UVvis spectra of MO using an UVvis spectrophotometer (UV
2100, Shimadzu). The PEC of MO under visible light irradiation was
carried out in a quartz reactor with samples serving as the photoanode, platinum foil serving as the cathode, and an Ag|AgCl|satd.
KCl electrode serving as the reference electrode. The bias potential applied on the photo-anode was 0.8 V (vs Ag/AgCl). All the
experiments were performed with magnetic stirring at 25 C and
continually bubbled with N2 .
3. Results and discussion

2.2. Preparation of N-doped WO3 nanoporous photoelectrodes

3.1. XRD

N-doped WO3 nanoporous photoelectrodes were prepared

by annealing anodic oxide layers in a NH3 /N2 gas mixture
(120 mL min1 ). The anodic oxide layers were also annealed in pure
N2 at 450 C as reference. Accordingly, modulating the gaseous
ammonianitrogen ratio was to detect its effect on N-doped WO3
nanoporous photoelectrodes.

The crystal structure signicantly inuenced the photocatalytic

activity of WO3 photoelectrodes. Due to crystal defect state, i.e. the
unbonded oxygen, which might become the recombination center
of photoelectron and hole, amorphous WO3 showed lower photocatalytic activity [38,39]. Fig. 1 shows the XRD patterns of undoped
WO3 and modied WO3 annealed at different temperature. The
WO3 lms annealed at 450 C in N2 show sharp diffraction peaks
at 23.3 , 23.8 and 24.6 , which suggest monoclinic WO3 phase
according to JCPDS data (JCPDS 43-1035). Similarly, the samples
annealed in NH3 /N2 form a monoclinic structure at 300 and 450 C.
At 550 C, the intensities of WO3 peaks obviously reduce and two
weak diffraction peaks in the regions 3743 which corresponds to
W2 N appears. Since the XRD indicates the presence of W2 N phase,
it is also determined that the oxygen sites are occupied by nitrogen atoms [40]. The higher temperature anneal at 650 C induces

2.3. Microstructure and chemical analysis

A eld-emission scanning electron microscope (FESEM, Sirion
200, FEI, Holland) was employed for the structural and morphological characterization of the as-prepared photoelectrodes. The
crystalline structure of the samples was measured by X-ray diffraction (XRD, D/Max2250, Rigaku, Japan). The chemical compositions

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Y. Liu et al. / Applied Surface Science 258 (2012) 50385045

Fig. 1. The X-ray diffraction patterns of nanoporous WO3 electrodes annealed at

different temperature.

a stronger intensity of W2 N with a further decrease in the intensity of the WO3 phase. It is reported that the formation of W2 N
and the loss of crystallinity in the WO3 induce deactivation of the
photoresponse [23,41].
3.2. XPS
The XPS spectra of undoped WO3 and N-doped WO3 photoelectrodes annealed at 450 C are shown in Fig. 2a. The surfaces of
N-doped WO3 photoelectrode are composed of tungsten, oxygen,
nitrogen and carbon contaminants. No nitrogen signal was detected
in the undoped WO3 sample whist weak nitrogen signals appeared
in N-doped WO3 samples. Fig. 2b shows the enlarge N 1s peaks
of the undoped WO3 and N-doped WO3 samples. In the case of Ndoped WO3 , there is a board peak observed from 392 to 402 eV. Two
well-dened peaks can be distinguished, which indicated the N 1s
binding energies were 399.75 and 395.59 eV, respectively. Usually
the peak at 396 eV corresponds to the bonding state of N W and the
one at 400 eV can be assigned to N that is surface bond with N or O,
which is in agreement with the ndings reported by Ghicov et al.
[42]. Considering that no W2 N was observed at this temperature
from the XRD pattern, it is suggested the fact that the substitution of O in WO3 by N element and formation of W O N band.
Therefore, one can conclude from the XPS results that the nitrogen was not only successfully implanted in the structure but it was
also present in a chemically bonded state, indicating that nitrogen is
successfully doped in the WO3 lattice annealed in NH3 /N2 at 450 C.
3.3. SEM
Fig. 3 shows the morphology of the samples over the range
anneal temperature. To illustrate the evolution, the sample before
heat treatment is also included here. Fig. 3a is top-view SEM image
of WO3 lm formed by anodization of W in the (NH4 )2 SO4 electrolyte with NH4 F. A highly ordered porous oxide structure is
present after anodization, where a typical pore size of approximately 70 nm is observed. These samples were then exposed to
a heat treatment in NH3 /N2 at different temperature. The sample
maintained its morphology for anneal in NH3 /N2 gas up to 300 C.
A further increase in temperature to 450 C causes an alteration in
the morphology, with WO3 nanorods growing randomly on surface
of the porous lms. However, it is quite clear, that at a anneal temperature of 550 C, a change in the morphology. The ordered porous
structure is deformed and consists of massive particles. It appears
that a compact layer forms with increasing in anneal temperature.

Fig. 2. (a) XPS spectrums of undoped and N-doped nanoporous WO3 electrodes
calcined at 450 C, and (b) XPS high-resolution spectra of N 1s peak for undoped and
N-doped WO3 electrodes.

The sample sintering in N2 at 450 C provided layer with morphology similar to the NH3 /N2 case, but with large feature size of the
particles, as shown in Fig. 3e.
3.4. Photoelectrochemical analysis
Little is known about the effect of chemical state of the N dopant
on the electronic properties of WO3 nanoporous photoelectrodes.
In order to understand the intrinsic electronic of properties Ndoped WO3 nanoporous photoelectrodes in electrolyte solution, we
performed electrochemical impedance measurement in the dark to
determine the capacitance of layers. Based on the MottSchottky
equation, the space charge layer capacitance (Csc /F cm2 ) of a semiconductor determined from measured impedance (C = 1/Z ) is
related to the applied potential (U/V):
1
2
Csc

2
0 qND

U Ufb

kT
q

where is the relative permittivity of the semiconductor (50 for

WO3 ) [43], 0 is the vacuum permittivity (8.85 1014 F cm2 ), q is
the electronic charge (1.60 1019 C), ND /cm3 is the donor carrier
density (for an n-type semiconductor), Ufb /V is the at band potential, k is the Boltzmann constant (1.38 1023 J K1 ), and T/K is the
Kelvin temperature, respectively. Assuming that the capacitance of
the Helmholtz layer can be neglected, the MottSchottky plots of

Y. Liu et al. / Applied Surface Science 258 (2012) 50385045

5041

Fig. 4. MottSchottky plots of undoped and N-doped nanoporous WO3 photoelectrodes. The capacitance was measured at 1 kHz of a frequency and 10 mV of
amplitude potential.

the WO3 layers annealed in N2 and N2 /NH3 at the AC frequency

of 1 kHz in a 0.5 M H2 SO4 aqueous electrolyte are shown in Fig. 4.
The positive slopes indicate that both of the samples are n-type
semiconductors. The Ufb values were provided from the x-intercept
and the donor density ND was estimated from the slope of the plot
2
(Csc
vs potential) using the relationship slope = 2/0 qND . The
donor concentrations were calculated to be 2.58 and 6.84 1022
for undoped and N-doped samples, respectively. The N-doped WO3
nanoporous photoelectrodes exhibited higher donor concentration
compared to the undoped sample due to N incorporation and/or
native defects such as W interstitials and O vacancies. Moreover, it
is found that the at band potentials were 0.25 and 0.31 V for the
N-doped and undoped WO3 , respectively. The Ufb of the N-doped
WO3 obviously shifts negatively in contrast to that of the undoped
WO3 , indicating a modied band structure by doping. Usually, the
more negative the at band potential, the better is the ability of
semiconductor lm to facilitate the charge separation [44].
In order to address the quantitative correlation between
N-doping and light absorption of the nanoporous WO3 photoelectrodes, the photocurrent response of the samples as a function of
wavelength of incident light was measured at a potential of 1.2 V
vs Ag/AgCl in a 0.5 M H2 SO4 solution. Photoaction spectra for the
undoped and N-doped WO3 photoelectrodes are compared in Fig. 5,
where the incident photon to electron conversion efciency (IPCE)
is plotted vs wavelength

IPCE (%) =

1240 jp
P

100

where jp is the photocurrent density (mA/cm2 ), P is the incident

photon ux density at the photoelectrode location (mW/cm2 ) and
 is wavelength (nm). With an onset of IPCE at 450 nm, the undoped
samples have strong photoresponse in the near-UV region but little
photoresponse in >450 nm ascribed to intrinsic band gap energy
of WO3 . In contrast, the samples at 450 C in NH3 /N2 (N-doping)
show substantial photo-activity in the visible light region from
400 to 600 nm in addition to strong photoresponse in the nearUV. These results clearly conrm that nitrogen can be successfully
doped in WO3 by annealed in NH3 /N2 , resulting in considerable

Fig. 3. SEM images of the (a) as-anodized WO3 electrode and annealed in NH3 /N2
(v/v = 1:2) at (b) 300 C, (c) 450 C, (d) 550 C, and in N2 at (e) 450 C, respectively.

5042

Y. Liu et al. / Applied Surface Science 258 (2012) 50385045

Fig. 5. Photoaction spectra (IPCE vs wavelength) of the nanoporous WO3 photoelectrodes, recorded in 0.5 M H2 SO4 at 1.2 V vs Ag/AgCl.

visible response. Additionally, more interesting is that the sample

annealed at 550 C in NH3 /N2 also extended its optical response to
600 nm, although the IPCE in UV region signicantly decreased.
To further quantify the PEC performance, systematic electrochemical measurements were carried out to evaluate the PEC
properties of photoanodes fabricated from the different WO3 samples in a 0.5 M H2 SO4 solution (pH 0). Fig. 6 shows a set of liner
sweep voltammagrams recorded on these WO3 layers in the dark
and with illumination of 100 mW/cm2 (AM 1.5). Dark scan liner
sweep voltammagrams from 0 to 1.6 V indicate a weak current in
the range of 108 A/cm2 . Upon illumination with a visible light
source, all samples exhibit pronounced photocurrent starting at
+0.4 V. In comparison to undoped WO3 annealed at 450 C in N2 ,
the N-doped samples annealed at 450 C in NH3 /N2 show a signicant enhancement in photoresponse with the photocurrent density
increasing from 2.8 to 3.3 mA/cm2 . There is no saturation of photocurrent observed at positive potential, indicating efcient charge
separation in nanoporous layers upon illumination [45]. Furthermore, it was demonstrated that the photocurrent density is strongly
affected by the temperature during anneal in NH3 /N2 from the

Fig. 7. The photocurrent density of WO3 nanoporous photoelectrodes annealed in

NH3 /N2 atmosphere with the different ratio at 450 C, recorded in 0.5 M H2 SO4 at
1.2 V vs Ag/AgCl.

temperature-dependence liner sweep voltammagrams collected

from the N-doped WO3 nanoporous photoelectrodes. The samples
annealed at 300, 450, 550 C showed 1.5, 2.3, 3.3 mA/cm2 at 1.6 V (vs
Ag/AgCl) on the front side illumination, respectively. The maximum
photocurrent was obtained with the sample annealed at 450 C and
photocurrent decreased with further increase of annealed temperature above 550 C. This tendency may be attributed to the crystal
phase conversion and the structure of WO3 layers. Recent studies
by Schmuki and co-workers [23] suggested that the formation of
W2 N and the loss of crystallinity in the WO3 induce deactivation of
the photoresponse.
To determine the optimized synthetic conditions for achieving
the highest photoelectrochemical performance, the WO3 photoelectrodes were annealed in NH3 /N2 atmosphere with the different
ratio. Effect of gaseous NH3 concentration on photocurrent density
can be seen from Fig. 7. The photocurrent increased with increasing the NH3 /N2 ratio to 1/2. Further increase in the NH3 /N2 ratio
resulted in a decrease in the photocurrent density. One possible
reason is that higher concentration of NH3 would increase the
efciency of nitrogen doping on WO3 layers. Increasing the nitrogen concentration will lower the quantum yields. In other words,
the nitrogen doping sites could also serve as recombination sites,
which will decrease photocurrent density [46,47]. So far, when the
NH3 N2 ratio was 1/2 (v/v), the optimum photoelectrochemical
performance could be obtained.
3.5. PC and PEC degradation of MO under visible light irradiation
According to the results of the photocurrent action measurement, the N-doped samples are expected to show the different
photocatalytic properties from those of pure WO3 . Thus, the photocatalytic activities of the samples were measured with visible light
( 400 nm) degradation of MO as model reaction. The photocatalytic (PC) degradation of MO follows pseudo-rst-order kinetics.
The kinetic
 constant k can be calculated from the linear transform
[48]ln

Fig. 6. Liner sweep voltammagrams, collected at a scan rate of 10 mV/s at applied

potentials from 0 to +1.6 V from the nanoporous WO3 photoelectrodes.

C0
Ct

= kt where C0 is the initial concentration of MO and

Ct is the concentration of MO at time t. The MO concentration

does not change for every measurement using various samples
under dark conditions without light illumination. Illumination in
the absence of WO3 photoelectrodes does not result in the photocatalytic decolorization of MO. Therefore, the presence of both

Y. Liu et al. / Applied Surface Science 258 (2012) 50385045

5043

Fig. 9. Degradation rates of MO by various processes on undoped and N-doped

nanoporous WO3 photoelectrodes under visible light irradiation.

Fig. 8. (a) Degradation rates of MO and (b) kinetic rate constants of various
nanoporous WO3 photoelectrodes under visible light irradiation.

illumination and WO3 photoelectrodes is necessary for the efcient degradation. These results also suggest that the degradation
decolorization of MO aqueous solution is caused by photocatalytic
reactions on WO3 photoelectrodes surface under the visible illumination.
Fig. 8 shows the comparison of photocatalytic activity of the
WO3 photoelectrodes annealed at different temperatures. It can be
seen that the calcination temperatures have a great inuence on
the photocatalytic activity of the WO3 layers annealed in NH3 /N2 .
At 300 C, the sample shows a relative low photocatalytic activity due to the weak crystallization of WO3 in the samples [38].
With increasing the calcination temperature to 450 C, the photocatalytic activity obviously increases owing to the enhancement
of WO3 crystallization and the decrease of defects in the samples.
At 450 C, the N-doped photoelectrode shows the highest photocatalytic activity and its k reaches 0.0459 min1 . The k was determined
to be 0.0352 min1 for the undoped sample. The photocatalytic
activity of the sample annealed in NH3 /N2 at 450 C exceeds that of
the sample in N2 by a factor of 1.3, which could be ascribed to the
N doping. With further increasing the calcination temperature to
550 C, the photocatalytic activity decreases. This is ascribed to the
following two causes. The rst cause is due to the WO3 changing
into W2 N, which has lower photocatalytic activity than WO3 [23].
The second cause is due to destroy of architectures and nanoporous

structures of WO3 photoelectrodes, resulting in the decrease of

photocatalytic activity [49].
The electrochemical (EC), PC and PEC process of MO in aqueous
solution under visible light irradiation are performed on undoped
and N-doped WO3 photoelectrodes. The experimental results are
displayed in Fig. 9. The corresponding kinetic constants and regression coefcients of MO degradation are listed in Table 1. It is obvious
that the EC process of MO is much slower than PC and PEC process,
suggesting that the EC degradation of MO could not rapidly react
without visible light irradiation. As a photocatalyst, WO3 results in
the effective photocatalytic degradation of MO. This is attributed
to the more effective separation of photogenerated electronhole
pairs and the higher internal surface area of the special nanoporous
structure [8]. When the bias potential of 0.8 V is applied to undoped
WO3 photoelectrode, PEC degradation rate of MO is approximately
2.2 times of PC degradation rate. It is found that PC and PEC degradation rate of MO on N-doped WO3 electrode are 1.3 and 1.6
times of that on pure WO3 layer. Obviously, N-doped WO3 shows
the highest decomposition rage in the PEC process, suggesting
that the applied bias potential inhibits the recombination of the
photogenerated electronhole pairs effectively and lengthens the
photogenerated carriers life [50]. Especially, PC degradation rate of
MO on N-doped WO3 electrode is almost equal to the PEC degradation rage of MO on undoped photoelectrode. With an appropriate
amount of nitrogen on WO3 , an efcient charge separation of
the photogenerated electronhole pairs can be accomplished [51].
These results are in accordance with that of photocurrent spectra.
The process of visible light photocatalytic oxidation of MO is
described in Fig. 9. First, holes in the N impurity level and electrons in conduction band were generated (Eq. (1)) under visible
light irradiation [52,53].
WO3 N + hv h+ + eCB

(1)

In the photocatalytic process, the hole and electrons will react

with molecule O2 and OH on the catalyst surface to form O2
superoxide anion radicals and OH radical [54], respectively (Eqs.
(2)(4)). The O2 radicals then interact with H2 O absorbed to produce more OH radical (Eq. (5)).
H2 O OH(surf) + H+

(2)

OH(surf) + h OH

(3)

eCB + O2 O2(surf)

(4)

2(surf)

+ H2 O OH + OH

(5)

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Y. Liu et al. / Applied Surface Science 258 (2012) 50385045

Table 1
PEC kinetic rate constants and regression coefcient of undoped and N-doped nanoporous WO3 photoelectrodes under visible light irradiation.
Process

Undoped WO3

PC
EC
PEC

N-doped WO3

Kinetic constant k
(min1 )

Correlation
coefcient, R2

Kinetic constant k
(min1 )

Correlation
coefcient, R2

0.0352
0.0124
0.0553

0.983
0.994
0.989

0.0473
0.0156
0.0903

0.992
0.995
0.991

the crystal lattice of WO3 . The microstructure and morphology of

WO3 nanoporous photoelectrodes were signicantly affected by
the temperature during the NH3 /N2 treatment. When the calcination temperature was as high as 550 C, the WO3 phase gradually
transformed to W2 N and the order porous structure is deformed.
IPCE studies of the N-doped WO3 nanoporous photoelectrodes
show a signicant enhancement in conversion efciency in the
visible light. The photocatalytic activity of as-prepared N-doped
WO3 nanoporous photoelectrodes was determined by degradation
of MO under visible light irradiation, and compared to the undoped
sample. The PC and PEC degradation rate of the N-doped WO3 photoelectrode annealed at 450 C in a NH3 /N2 (v/v = 1/2) gas mixture
are 1.3 and 1.6 times of that on undoped photoelectrode, respectively.

Fig. 10. Schematic diagram of the interface charge-carrier transfer of photocatalysis and photoelectrocatalysis for N-doped nanoporous WO3 photoelectrodes under
visible irradiation.

Finally, these OH radicals react with MO mineralize it (Eq. (6)).

OH

+ MO CO2 + H2 O

(6)

For the photocatalytic reaction, the lower recombination rate

of photogenerated electrons and holes of WO3 photoelectrode
induces the signicant enhancement of the photocatalytic activity. A feasible mechanism of the photoelectrocatalysis is shown in
Fig. 10. The photogenerated electrons are forced to transfer to the
counter electrode by applying an anodic bias potential to the WO3
working electrode and then reduce the oxygen absorbed on the surface of counter electrode to form O2 , while the photogenerated
holes in the WO3 photoelectrode react with H2 O to form OH. The
photoelectrocatalytic reaction is summarized in the following Eqs.
(7)(10):
Photoanode:
WO3 N + h h+ + eCB
+

H2 O + h

OH

+H

(7)
(8)

Cathode (counter electrode):

eCB + O2 O2(surf)

O
2(surf)

+ H2 O OH + OH

(9)
(10)

A positive potential applied on WO3 photoelectrode can inhibit

the recombination of eCB and h+ . While the working electrode is
N-doped WO3 photoelectrode, N doping extended the visible light
absorption edge and the electrons were excited form the N impurity
level to the conduction band, resulting in the enhancement of the
photoelectrocatalytic activity.
4. Conclusions
In summary, we have synthesized N-doped WO3 nanoporous
photoelectrode by one step annealing the anodic oxide layers
in a NH3 /N2 gas mixture. The results of XRD and XPS demonstrated that the nitrogen element was indeed incorporated into

Acknowledgment
This study was supported by the National High Technology
Research and Development Program of China (863 Program, No.
2011AA050528) and the National Nature Science Foundation of
China (nos. 51072232 and 21171175).
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