international journal of hydrogen energy 34 (2009) 3250–3257

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Hydrogen generation under sunlight by self ordered TiO2

nanotube arrays

Zhaoyue Liua, Batric Pesicb, Krishnan S. Rajaa, Raghu R. Rangarajua, Mano Misraa,*
a
Chemical and Metallurgical Engineering, MS 388, University of Nevada, Reno, NV 89557, USA
b
Material Science and Engineering, University of Idaho, Moscow, ID 83944, USA

article info abstract

Article history: Highly ordered TiO2 nanotube arrays generate a considerable interest for hydrogen
Received 10 January 2009 generation by an electrochemical photocell, since ordered architecture of nanotube arrays
Received in revised form provides a unidirectional electric channel for electron’s transport. Here, we report the
19 February 2009 hydrogen generation by highly ordered TiO2 nanotube arrays under actual sunlight in KOH
Accepted 20 February 2009 electrolyte. The two-electrode electrochemical cell included an adjustable anode
Available online 17 March 2009 compartment capable of tracing the trajectory of the sun and a set of alkaline batteries
connected with a rheostat for application of external bias. The results showed that the
Keywords: photocurrent responses of nanotube arrays match well with the intensity of solar irradi-
Titanium dioxide ance on a clear summer day. Addition of ethylene glycol into KOH electrolyte as a hole
Nanotube scavenger enhanced the rate of hydrogen generation. A maximum photocurrent density of
Hydrogen generation 31 mA/cm2 was observed at 13:30 h, by focusing the sunlight with an intensity of 113 mW/
Sunlight cm2 on the surface of the TiO2 nanotube arrays in 1 M KOH electrolyte with 10 vol%
ethylene glycol under an applied bias of 0.5 V. The observed hydrogen generation rate was
4.4 mL/h cm2 under the focalized solar irradiance with an intensity between 104 mW/cm2
and 115 mW/cm2 from 10:00 to 14:20 h.
ª 2009 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights
reserved.

1. Introduction
Hydrogen is a clear and sustainable energy carrier, which is
a possible alternate for the fossil fuel to resolve the energy
problems in the future [1–4]. Pioneered by Fujishima and
Honda in 1972 [5], photocatalytic water splitting using tita-
nium dioxide (TiO2) photoelectrode under solar light presents
a great potential for hydrogen generation. TiO2 has been
investigated widely as an anodic material of photocell, due to
its high photocatalytic activity, photochemical stability and
nontoxicity [6–9]. Although single crystal TiO2 presents a high
activity for water splitting, polycrystalline TiO2 film is desired
from the practical standpoint of realizing a large-scale
photocell [10]. However, polycrystalline particulate TiO2 thin
film suffers from structural disorders and vast grain bound-
aries, which adversely affect charge’s transportation and
photoconversion efficiency [11].
In recent years, highly ordered TiO2 nanotube arrays
exhibit a promising potential for the anodic material of
photocell [12–20]. The vertically oriented architecture of the
nanotube arrays provides a unidirectional electric channel for
electrons transport, which can help to reduce the charge
recombination. In one of our recent studies [21], we found that
organic compounds, for example ethylene glycol, in the elec-
trolyte could further suppress the charge recombination in
TiO2 nanotube arrays and enhance its activity for hydrogen
generation. Although a large number of reports are available
on the application of TiO2 nanotube arrays for hydrogen

* Corresponding author. Tel.: þ1 775 784 1603.

E-mail address: misra@unr.edu (M. Misra).
0360-3199/$ – see front matter ª 2009 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijhydene.2009.02.044
 international journal of hydrogen energy 34 (2009) 3250–3257
generation under artificial sunlight, there is no information
about its application under real sunlight to the best of our
knowledge. Herein, we investigate the hydrogen generation by
highly ordered TiO2 nanotube arrays in KOH electrolyte with
and without ethylene glycol under actual sunlight, which
provides some useful information for the possible practical
application of TiO2-based photocell.
2. Experimental section
2.1. Synthesis of highly ordered TiO2 nanotube arrays
Self ordered TiO2 nanotube arrays were prepared by an elec-
trochemical anodization under ultrasonic field in a two-elec-
trode electrochemical cell [22,23]. A 16 mm diameter titanium
foil loaded on to a PEEK specimen holder exposing only 0.7 cm2
area was used as a working electrode, and a platinum flag with
a size of 3.8 cm2 was used as a counter electrode. The distance
between the working and counter electrodes was kept at 2 cm.
Anodization of titanium foil was performed at 20 V for 45 min
in 0.135 M ammonium fluoride (Fisher Scientific) in ethylene
glycol (Fisher Scientific) containing 10 vol% water. The voltage
was applied by a dc power supply (Agilent, E3649A). The as-
prepared TiO2 nanotube arrays were annealed at 500  C in
hydrogen atmosphere for 3 h to convert amorphous TiO2 to
crystalline phase. The morphology and structure of the
nanotube arrays were characterized by a Hitachi S-4700 field
emission scanning electron microscope and a high resolution
transmission electron microscope (JEOL 2010F). The optical
absorbance behavior of TiO2 samples was characterized using
a UV–vis photospectrometer (Model: UV-2401 PC, Shimadzu
Corporation, Kyoto, Japan). Photoelectrochemical potentio-
dynamic and electrochemical impedance spectroscopy
studies were carried out using a three-electrode configuration
(Ag/AgCl in saturated KCl as reference electrode) and
a computer-controlled potentiostat (Model: SI 1286, Schlum-
berger, Farnborough, England). A 300 W solar simulator
(Model: 69911, Newport-Oriel Instruments, Stratford, CT, USA)
equipped with an AM 1.5 filter was used as a light source.
Mott–Schottky analysis was performed by determining the
interfacial capacitance at 1000 Hz from the impedance
measurements by superimposing an ac signal of 10 mV
amplitude on the dc applied potential which varies from 0.2 V
to 1.5 V in steps of 50 mV with a time interval of 2 s.
The TiO2 nanotubular array samples prepared in ethylene
glycol based electrolyte were modified with carbon incorpo-
ration after annealing in hydrogen environment. In order to
understand the effect of carbon modification, TiO2 nano-
tubular samples without carbon incorporation were prepared
by anodization of Ti foil in 0.5 M H3PO4 þ 0.135 M NH4F solu-
tion at 20 V for 45 min. These samples were annealed at 500  C
in oxygen atmosphere for 3 h and designated as unmodified
TiO2 nanotubes (control samples for comparison with carbon
modified samples).
2.2. Photocell for hydrogen generation under sunlight
As shown in Fig. 1, our homemade electrochemical photocell
for hydrogen generation was a two-electrode configuration
3251
with two separate compartments connected by an 1 inch
diameter fine glass frit. The anode was TiO2 nanotube arrays
with a geometric area of 0.7 cm2. A copper wire was attached
on the backside of the titanium foil using a conductive silver
paste. The exposed titanium foil and copper wire assembly
were insulated by a thick coating of epoxy resin. The cathode
was a platinum wire spiral, which was spot welded to
a stainless steel rod. 1 M KOH (Fisher Scientific) solution with
and without 10 vol% ethylene glycol were used as electrolyte.
The sunlight was focused on the anode by a lens with a focal
length of 75 mm. When focused, the area of the sunlight
illumination was about 0.03 cm2. As a result, the intensity of
sunlight was enhanced by about 120 times compared with the
natural sunlight. The anode compartment could be adjusted
to focus the sunlight on the TiO2 electrode following the
trajectory of the sun. The cathode compartment was provided
with a glass burette and a syringe assembly. The syringe was
used for raising the electrolyte level in the burette before start
of the experiment. The Pt-stainless rod electrode was inserted
through the burette such that all the hydrogen gas evolving at
the cathode could be collected in the burette displacing the
electrolyte level. The volume of hydrogen gas was measured
by directly reading the variation of electrolyte level in the
burette. An adjustable voltage provided by a battery was
applied between the anode and cathode. The values of
external voltage and the photocurrent were directly read from
two multimeters provided in the electric circuit. The intensity
of the light was measured by a radiant power and energy
meter (Model 70260, Newport Corporation, Stratford, CT, USA)
and a thermopile sensor (Model: 70268, Newport).
3. Results and discussion
Fig. 2(a) shows the morphology of carbon modified TiO2
nanotube arrays after annealing in hydrogen atmosphere. The
nanotubes are about 600 nm long (Fig. 2(a), inset). The inside
diameter of the nanotubes is in the range of 50–60 nm and the
wall thickness is in the range of 8–13 nm (Fig. 2(b)). From the
cross sectional image (inset of Fig. 2(a)), we can see TiO2
Fig. 1 – Homemade photocell for hydrogen generation
under sunlight. (1) TiO2 nanotube arrays anode, (2) Pt wire
spiral cathode, (3) gas burette, (4) multimeter for voltage, (5)
multimeter for current, (6) focus lens, (7) battery, (8) voltage
adjust button.
3252 international journal of hydrogen energy 34 (2009) 3250–3257

R(110)

Ti
A(101)
Intensity, a.u

R(101)

A(105)
Ti

R(111)

A (200)
R(210)

A(220)
20 30 40 50 60
2-theta, degree

Fig. 3 – Glancing angle XRD pattern of the carbon modified

TiO2 nanotubular arrays.

will be w412 nm. Whereas, the unmodified TiO2 samples

Fig. 2 – (a) FESEM image of the surface morphology of the
carbon modified TiO2 nanotube array. The inset shows the
cross section indicating the length of the nanotubes. (b)
TEM image of the carbon modified TiO2 nanotubes. The
inset shows the high resolution lattice fringes. The lattice
spacing corresponds to (110) planes of rutile.
showed a clear onset of optical absorbance at about 390 nm
due to anatase phase and a slight hump at 600 nm possibly
due to adsorbed hydroxyl ions. A considerable red-shift in
absorption wavelength in the visible region is observed for the
TiO2 nanotubes formed in the ethylene glycol based electro-
lyte. During the anodization process, ethylene glycol is
oxidized to carbonate type species which get adsorbed on the
walls of the nanotubes as an outer layer. Upon annealing in
the hydrogen atmosphere, the carbonate species are possibly
reduced to carbon species and diffuse into the nanotube walls.
A significant absorption shoulder starting at 560 nm is attrib-
uted to the band gap states created by incorporation of carbon
species in the nanotubes. The band gap states could be oxygen
vacancies introduced by annealing in hydrogen or doping of
carbon in the TiO2 lattice substituting with oxygen sublattice.
The carbon modified TiO2 nanotubes show an indirect band
gap of 2.2 eV [15]. Fig. 5 shows a typical XPS result of the sub-
surface analysis of the carbon modified TiO2 nanotubes after
1.4
Optical absorbance, arb. unit

1.2 Carbon modified TiO2 nanotubes

nanotubes are vertical to the conductive titanium substrate. 1

Resembling a perpendicular ZnO nanowire structure [24], the
vertically oriented architecture of the ordered nanotube 0.8

arrays can provide a unidirectional electric channel for the

0.6 3.2 eV
transport of photogenerated electrons. The TiO2 nanotubes
without carbon modification also showed similar morphology 0.4
[14]. Therefore, TiO2 nanotube array is a promising anodic 2.21 eV
TiO2 nanotubes
material for hydrogen generation by photocell. Inset of Fig. 2 0.2 without carbon
(b) illustrates the lattice fringes associated with (110) planes of
the rutile phase. The nanotubes after annealing at 500  C 0
200 300 400 500 600 700 800
contain a mixture of anatase and rutile phases as determined
Wavelength, nm
from the glancing angle XRD analysis (Fig. 3). Fig. 4 shows the
optical absorbance behavior of the TiO2 nanotubes with and Fig. 4 – Photoabsorption characteristics of TiO2 nanotubes
without carbon modification. An absorption shoulder is with and without carbon modification by diffuse
observed at wavelengths longer than 400 nm for the carbon reflectance UV–vis photospectroscopy. The shoulder at
modified samples. Since these nanotubes contained mixture wavelengths longer than 400 nm corresponds to band gap
of rutile (band gap: 3.01 eV) and anatase (band gap: 3.2 eV), it is states introduced by incorporation of carbon species in the
expected that the take-off wavelength for optical absorption TiO2 nanotube walls.
 international journal of hydrogen energy 34 (2009) 3250–3257 3253

400
285.6 eV C1s
350

O 1s
300 287.2 eV

Counts
250
200
150
100
50

F 1s

Ti 2s
O KLL
0
290 288 286 284 282 280
Binding Energy, eV

C 1s

Ti 3s
Ti 3p
O 2s
1000 900 800 700 600 500 400 300 200 100 0
Binding Energy (eV)

Fig. 5 – XPS analysis of the carbon modified TiO2 nanotubular sample after sputtering out 2 nm thick material using argon
ions. The inset shows the high resolution C-1s spectrum. The peak at 285.6 eV corresponds to adventitious or graphitized
carbon and 287.2 eV is associated with Ti–C or carbonate type carbon.

argon ion sputtering of 2 nm thick material from the surface. vs Ag/AgCl for carbon modified and unmodified samples
A clear C-1s peak is observed indicating presence of carbo- respectively. When illuminated, the open circuit potentials
naceous species. High resolution analysis of the C-1s peak shift in the negative direction to about 0.95 V and 0.85 V
indicated a doublet; one at 285.6 eV binding energy and the for carbon modified and unmodified samples respectively.
other at 287.2 eV. The former binding energy is associated
with adventitious carbon or graphitized carbon and latter a 0
Carbon modified
peak corresponds to the presence of Ti–C type doped carbon -0.1 Illumination on
[15]. The doped carbon constituted 30.3% of the total carbon Without carbon
-0.2
present in this analysis. The C-1s peak area can be estimated
Potential, V Ag/AgCl

Illumination off Illumination on

-0.3
as 6.2% of the total Ti-2p and O-1s peak areas, which give
about 1.87% of doped carbon. It should be noted that the -0.4

reported analysis of the carbon in the TiO2 nanotubes is only -0.5

semi-quantitative since accurate determination of carbon -0.6
requires very tedious procedure. -0.7
In principle, the hydrogen generation by TiO2 photoanode
-0.8
under UV light in KOH electrolyte proceeds as follows:
-0.9
-1
0 50 100 150 200 250 300
TiO2 þ 2hn (UV) /2e þ 2 hþ (1)
Time, s

2OH þ 2 hþ / H2O þ 1/2O2 at the anode (2) b 3

Illuminated
Photocurrent density, mA/cm2

2.5
 
2H2O þ 2e / H2 þ 2OH at the cathode (3) Carbon modified
2
The overall cell reaction is
1.5

H2O / H2 þ 1/2O2 (4) 1

Without carbon

Based on above reactions, we can deduce that the gener- 0.5

Dark
ation of one hydrogen molecule from water requires two
0
photogenerated electrons to flow from TiO2 anode to platinum -1 -0.8 -0.6 -0.4 -0.2 0 0.2
cathode. Therefore, we can evaluate the ability of TiO2 nano- Potential, VAg/AgCl
tube array for hydrogen generation by measuring its
photocurrent. Fig. 6 – Photoelectrochemical behavior of TiO2 nanotubular
Fig. 6(a) shows the open circuit potential transient during arrays with and without carbon modification in 1 M KOH
interrupted AM 1.5 illumination of the carbon modified and solution under AM 1.5 illumination. (a) Potential transient
unmodified TiO2 nanotubes. Without illumination, the open with and without light illumination; and (b) Photocurrent
circuit potential is more positive at around 0.3 and 0.25 V generation as a function of bias potential.
3254 international journal of hydrogen energy 34 (2009) 3250–3257

The value of potential shift (about 0.60 V) is the photo- equilibrium in dark. Whereas, the increase in the photo-
potential which is also an indication of amount of band generated electron concentration is only a fraction of the
bending of the TiO2 semiconductor in the electrolyte system original concentration under thermal equilibrium in dark.
before illumination. The shift in the potential is abrupt Therefore, the excess holes require time to find excess elec-
initially followed by a slower kinetic before it reaches trons for recombination. Because of this diffusion controlled
a steady value for both the samples. Deposition of the inci- process, the recovery of the open circuit potential after
dent light on the semiconductor generates electron–hole switching-off the light is slower as observed in Fig. 6(a). In
pairs. The electrons drift to the back contact because of an case of the unmodified TiO2, the recovery of potential to the
electric field present in the space charge layer due to band initial dark OCP value occurred at a faster rate than that of
bending until the band becomes flat. The holes preferentially the carbon modified sample. This could be attributed to the
move to the surface of the semiconductor/electrolyte inter- lower concentration of band gap states and surface states
face where they get consumed by the reaction of type available in the unmodified TiO2 samples that act as more of
OH þ hþ / OH . The surface area of the TiO2 nanotube

trap sites than as recombination centers.
arrays is very large. Therefore, consumption of holes is Fig. 6(b) shows the photocurrent density generated by the
envisaged to occur at a faster rate. Since the potential carbon modified and unmodified TiO2 nanotube arrays in 1 M
continues to shift in the negative direction, it is assumed that KOH electrolyte under the illumination of AM 1.5 light. The
the electron trap sites are filled initially at a faster rate and dark current upon interruption of the illumination is only
then the rate is slowed down because of the competition 10–30 mA/cm2 depending on the applied bias potential for the
between remaining trap sites and recombination centers. The carbon modified samples. Similar dark current density is
potential reaches steady state when all the reversible elec- observed for the unmodified sample. The photocurrent
tron trap sites are filled. When the illumination is inter- density of the carbon modified sample increases with
rupted, the potential shifts to positive direction which occurs increase in the applied potential and almost reaches
by the recombination of excess electrons and holes generated a plateau like behavior at potentials more positive than
by the photoconversion process. The recovery of dark open 0.5 V vs Ag/AgCl. The unmodified sample shows much
circuit potential occurs at a slower rate that depends on the lower photocurrent density. The superior photo-
minority carrier lifetime. Since TiO2 nanotubes show n-type electrochemical behavior of the carbon modified sample can
behavior, holes are the minority carriers. Even though equal be explained by the results of electrochemical impedance
number of electrons and holes are photogenerated, the spectroscopy as shown in Fig. 7(a) and (b). The Nyquist plot,
increase in the hole concentration is many order of magni- reactance (imaginary impedance) vs real impedance, of the
tude higher than its original concentration under thermal carbon modified TiO2 nanotube arrays in the KOH electrolyte

a -5000
b
-4500
1.6E+10
1.4E+10
-4000
1.2E+10
1/C2, cm4/F2

1.0E+10
-3500
Imaginary Impedance, Ohm

8.0E+09
6.0E+09
-3000
4.0E+09
Not illuminated 2.0E+09
-2500
0.0E+00
-1 -0.9 -0.8 -0.7 -0.6 -0.5 -0.4 -0.3 -0.2
-2000
Potential, VAg/AgCl
Illuminated with AM
-1500
1.5 light

-1000

-500

0
0 500 1000 1500 2000
Real Impedance, Ohm

Fig. 7 – Electrochemical impedance behavior of carbon modified TiO2 nanotubes in 1 M KOH solution with and without
illumination of AM 1.5 light. (a) Nyquist plot with and without illumination under open circuit condition; and (b) Mott–
Schottky plot at 1000 Hz without illumination.
 international journal of hydrogen energy 34 (2009) 3250–3257 3255

at open circuit potential with and without illumination indi- -8.E+04

cate that the charge transfer resistance (real impedance) is without carbon
not affected by the illumination. However, the diffusion -7.E+04
controlled Warburg type impedance is considerably

Imaginary Impedance, Ohm

decreased upon illumination, which could be attributed to -6.E+04 Dark, OCP
the photoconductivity of the material. Fig. 7(b) shows the
Mott–Schottky plot and a typical n-type behavior can be -5.E+04

Imaginary Impedance, Ohm

-4000
observed. From the slope of the plot and geometric area of the
electrode, the calculated charge carrier density is about -4.E+04 -3000

3.2  1019/cm3. Based on this charge carrier density, the space

-2000
charge layer thickness during anodic polarization of the TiO2 -3.E+04
nanotubes at 0.5 V is calculated to be about 12.1 nm -1000

(considering the flat band potential as 0.95 V). If we consider -2.E+04 0

0 1000 2000 3000 4000 5000
that the band bending occurs across the nanotube wall Real Impedance, Ohm
thickness rather than across the nanotube length (this -1.E+04
assumption can be valid if the electrolyte penetrates the
nanotube interior), the nanotubes with a wall thickness of 0.E+00
0.E+00 2.E+04 4.E+04 6.E+04 8.E+04
8–13 nm cannot support the band bending beyond a certain
polarization. Therefore, the charge separation process is not Real Impedance, Ohm
enhanced above 0.5 V and the photocurrent reaches Fig. 8 – Electrochemical impedance behavior of TiO2
a plateau value. Since the open circuit potential under illu- nanotubes (without carbon modification) in 1 M KOH
mination is 0.95 V, application of 0.5 V in the anodic direc- solution with and without illumination of AM 1.5 light.
tion (positive polarization) will be in the plateau regime of the Nyquist plot without illumination under open circuit
photocurrent generation. Based on this experimental value, it condition (OCP) and inset shows the Nyquist plot after
is decided that the outside testing under actual sunlight will illumination at OCP.
be carried out with 0.5 V external bias using a battery system.
Fig. 8 shows the complex plane electrochemical impedance of
the unmodified TiO2 samples. The impedance is at least an
order of magnitude higher than that of carbon modified Fig. 10 shows the current/voltage curves of carbon modi-
samples under dark condition. Upon illumination, the fied TiO2 nanotube arrays in 1 M KOH electrolyte with 10 vol%
impedance of the unmodified sample decreases considerably, ethylene glycol under dark and sunlight (13:30 at noon with
however, the value is much higher than that of the carbon a solar irradiance intensity of 113 mW/cm2). The current of
modified sample under similar experimental conditions. TiO2 nanotube arrays in the dark between 0.6 V and 2.0 V
Therefore, the enhanced photoactivity of the carbon modified external voltage is rather low (<0.13 mA/cm2), which means
samples could be attributed to the lower electrochemical no hydrogen is generated. Under the intensified sunlight, the
impedance and presence of band gap states that enhance current increases significantly. The onset for the photocurrent
light absorbance in the visible region (up to 2.2 eV). is at 0.6 V. Without application of any external voltage (0 V
We investigated the photocurrent responses of carbon
modified TiO2 nanotube arrays at different operation time on
one clear summer day at þ0.5 V external voltage in 1 M KOH 40 14
with and without 10 vol% ethylene glycol. As shown in Fig. 9,
35 12
in both electrolytes, the photocurrent responses increase first
Photocurrent, mA/cm2

Intensity of Focalized
30
and then decrease with time, which match well with the
Sunlight W/cm2

10
intensity of solar irradiance on one day. The addition of 25
8
10 vol% ethylene glycol into KOH electrolyte can enhance the
20
photocurrent greatly. As discussed in our previous paper [21], 6
15
organic substance in the electrolyte can act as hole scavenges
4
(i.e. sacrificial electron donor), which can suppress the charge 10
recombination in the UV-excited TiO2 nanotube arrays and 5 2
increase the photocurrent. Originally, organic pollutants were
0 0
added to the electrolyte to improve the hydrogen generation
9:00 10:00 11:00 12:00 13:00 14:00 15:00 16:00 17:00
of polycrystalline particulate TiO2 electrode [25]. In 1 M KOH
Operation Time
electrolyte with 10 vol% ethylene glycol, a maximum photo-
current of 31 mA/cm2 is obtained at 13:30 at noon with a solar Fig. 9 – Photocurrent responses of carbon modified TiO2
irradiance intensity of 113 mW/cm2, which is 2.2 times as nanotube arrays at D0.5 V external voltage under sunlight
much as that in 1 M KOH electrolyte (14 mA/cm2). Since the in KOH electrolyte with (hollow circle) and without (solid
sunlight can be focalized on the anode surface at any time by circle) ethylene glycol on two different days. The intensity
adjusting the anodic compartment, we believe the maximal of focalized sunlight in these two days is also shown in the
photocurrent results from the strongest intensity of UV light figure (Marker styles correspond with that of photocurrent
in the sunlight at noon. responses).
3256 international journal of hydrogen energy 34 (2009) 3250–3257

60
4. Conclusions
50
In summary, we have applied highly ordered carbon modified
Current, mA/cm2

40 TiO2 nanotube arrays for hydrogen generation under actual

sunlight. The photocurrent response of nanotube arrays
30
matches with the intensity of solar irradiance. In 1 M KOH
20 electrolyte with 10 vol% ethylene glycol, at þ0.5 V external
voltage, we can get a maximum photocurrent density of
10 31 mA/cm2 when the sunlight is focalized with an intensity of
113 W/cm2 on the surface of nanotube arrays. Correspond-
0 ingly, we have obtained an average hydrogen generation rate
-0.6 -0.2 0.2 0.6 1 1.4 1.8 2.2
of 4.4 mL/h cm2 under a solar irradiance with an intensity
Voltage, V
between 104 mW/cm2 and 115 mW/cm2 from 10:00 am to
Fig. 10 – Current/voltage curves of carbon modified TiO2 14:20 pm, including some contributions from the external
nanotube arrays in KOH electrolyte with 10 vol% ethylene voltage.
glycol under dark (hollow circle) and sunlight (solid circle).

external voltage), a photocurrent of 6.6 mA/cm2 is generated
under the intensified sunlight. Increasing the external voltage
can enhance the photocurrent. At 2.0 V external voltage, we
can get a photocurrent as high as 51.2 mA/cm2. The transport
of photogenerated electrons is suggested to be driven by the
concentration gradient of the electrons in the nanotube array
layer [26].
We collect the hydrogen gas using carbon modified TiO2
nanotube arrays at þ0.5 V external voltages under sunlight in
1 M KOH with 10 vol% ethylene glycol. Fig. 11 shows the
relation between the total hydrogen volume and the operation
time. We can collect 0.6 mL hydrogen gas (19 mL/cm2) using
this present photocell under a solar irradiance from 10:00 am
to 14:20 pm with an intensity between 104 mW/cm2 and
115 mW/cm2. Normalizing this hydrogen volume to the time,
we can get an average hydrogen generation rate of 4.4 mL/
h cm2. It should be noted that this generation rate of hydrogen
includes some contributions from the external battery. Based
on the photocurrent differences at zero and þ0.5 V voltage in
Fig. 10, we can calculate that the contribution from external
voltage is about 76%.
25
Hydrogen Volume, mL/cm2
Acknowledgment
This work has been sponsored by the U.S. Department of
Energy through DOE Grant No: DE-FC36-06GO86066.
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